Precision fragmentation assemblages and olefin polymerization catalysts made therefrom

ABSTRACT

A precision fragmentation assemblage is disclosed, along with precision fragmentation assemblage catalysts derivable therefrom. A method for the preparation of a precision fragmentation assemblage is also disclosed, along with a method for preparing precision fragmentation assemblage catalysts from precision fragmentation assemblages. A method is further disclosed for using precision fragmentation catalysts in the polymerization of olefins to produce polyolefins.

CROSS REFERENCE TO RELATED PATENT APPLICATIONS

This is a non-provisional application of prior pending U.S. provisionalapplication Ser. No. 60/440,142 filed Jan. 15, 2003.

The present invention relates to a precision fragmentation assemblage(PFA) and olefin polymerization PFA catalyst made therefrom. The presentinvention further relates to a method for preparing the PFA, forpreparing the PFA catalyst, and to a method of using the PFA catalyst toprepare polyolefins.

In the early 1950s, Ziegler discovered that alpha-olefins could bepolymerized at low pressure in the presence of metal catalysts. Thefirst homogeneous polymerization catalyst Cp2TiCl2-AlEt2Cl was reportedwithin a few years. Following this initial discovery and development ofwhat came to be known as Ziegler-Natta catalysts, an intense effortensued aimed first at improving catalyst stability and activity, andlater at expanding the types of α-olefin that could be prepared. It wasfound that partially hydrolyzed aluminum alkyls, in particularmethylalumoxane (MAO), could greatly increase the activity of the oftransition metal catalysts, especially of zirconocene complexes. Inaddition, other activators such as fluoroaryl borates augmentatedcatalyst performance.

Although many of the catalysts for olefin polymerization, includingsingle-site metallocenes, are capable of performing as homogeneouscatalysts for solution polymerization in non-nucleophilic organicsolvents such as toluene or aliphatic hydrocarbons, the range ofpolyolefins that can be achieved in homogeneous systems is limited.Commercial polymerization processes using soluble catalysts are mostlythose in which the lower-crystallinity polymers (e.g., elastomers andvery low-density ethylene copolymers) produced are soluble in thereaction medium. Production of higher density or higher crystallinitypolyolefins via slurry, bulk-monomer, or gas-phase processes results ininsoluble product. In batch polymerization, the polyolefin particlestend to be non-uniform in size. In economically desirable continuousprocesses, this non-uniformity manifests itself in reactor fouling. As aresult, catalyst systems based on insoluble carriers that can be fedinto the reactor smoothly without clumping were sought.

Insoluble carriers that have been developed include inorganics magnesiumchloride and silica. Organic polymeric particles have also been used assupports. Although metal catalysts and activators supported by suchsystems may be capable of catalyzing olefin polymerization, producingpolyolefins efficiently, these supported catalysts are prone to gross,uneven fragmentation during reaction. Instead of a single polyolefinparticle being formed from a single supported catalyst particle,multiple particles form. Instead of fragmenting smoothly to form verysmall, uniformly sized pieces of supported catalyst, uniformlydistributed throughout the growing polyolefin particle, some smallerpieces of the original supported catalyst particles completely detach toform fines which foul the polymerization reactor, causing frequent downtime with attendant lost revenue. Further negative features are that thefines, which are out-of-specification on the small side represent lostyield, and that the overall bulk particle size distribution of thepolyolefin product broadens, often beyond the limits of acceptability.In addition, those smaller pieces of the original supported catalystthat do not detach from the original catalyst particle are often ofwidely differing size, introducing inhomogeneities within the growingpolyolefin particle and reducing polyolefin yield.

U.S. Pat. No. 6,013,594 to Yang, et al., discloses polymeric supportparticles formed by spray drying microparticles which are suspended in aliquid medium, such as water or a hydrocarbon diluent. Although the sizeof Yang's microparticles does tend to determine pore size in the spraydried particles thus formed, spray dried particles formed in this wayhave a broad bulk particle size distribution. Furthermore, finestypically form during spray drying, some of which cling to the largerbulk particles only to detach from those larger particles prior to andduring olefin polymerization, thus forming undesirably small polyolefinbulk particles and causing reactor fouling. In addition, while it isdesirable to prepare hard, highly crosslinked microparticles to minimizethe extent to which they imbibe solvents and swell so that interstitialspace, and therefore porosity, is maintained during catalyst loading andolefin polymerization, it is those very highly crosslinked particlesthat cause the greatest amount of dust formation in spray dryers. Suchdust formation is well known to decrease yield of desired bulkparticles, to increase the risk of explosion, and to clog bag housessuch that costly spray dryer shutdowns become frequent.

We have, surprisingly, discovered that the problems enumerated supra maybe overcome by assembling fragmentation domains, by aqueous coagulationor other agglomeration means, to produce bulk particles. Monomers areadded to these bulk particles before, during, or after coagulation.Subsequent polymerization produces precision fragmentation assemblages(PFAs) which can then be loaded with catalytic components and,optionally, activator components to produce precision fragmentationassemblage catalysts (PFA catalysts) suitable for catalyzing olefinpolymerization. The presence of a connecting phase, of preciselycontrollable amount, composition, and morphology within the precisionfragmentation assemblage, allows elimination of detached fines andcontrol of stresses within the PFA catalyst during olefinpolymerization, particularly during the critical early stages.Catastrophic fragmentation is avoided. One PFA catalyst particleproduces only one appropriately larger polyolefin particle. Specializedparticle formation processes, e.g., “spheroid” coagulation and “jetting”processes, form spherical PFA particles having a narrow bulk particlesize distribution which can be converted to PFA catalysts, which, inturn, can be used to produce polyolefin bulk particles having narrowparticle size distributions.

One aspect of the present invention relates to a precision fragmentationassemblage, wherein said assemblage comprises:

-   -   (A) a plurality of fragmentation domains; and    -   (B) one or more fragmentation zones;        -   wherein said fragmentation domain comprises at least one            first polymer; and        -   wherein said fragmentation zone comprises:            -   (i) one or more connecting phases;            -   (ii) optionally, one or more pore phases; and            -   (ii) optionally plural polymeric nanoparticles; and            -   wherein said connecting phase comprises at least one                second polymer; and        -   wherein said nanoparticles comprise at least one third            polymer.

A second aspect of the present invention relates to a precisionfragmentation assemblage catalyst, wherein said catalyst comprises:

-   -   (A) a precision fragmentation assemblage; and    -   (B) at least one catalytic component;    -   wherein said precision fragmentation assemblage comprises:        -   (i) a plurality of fragmentation domains; and        -   (ii) one or more fragmentation zones;        -   wherein said fragmentation domain comprises at least one            first polymer; and        -   wherein said fragmentation zone comprises at least one            connecting phase, said connecting phase comprising at least            one second polymer.

A third aspect of the present invention relates to a precisionfragmentation assemblage catalyst further comprising at least oneactivator component.

A fourth aspect of the present invention relates to an olefinpolymerization process, wherein said olefin polymerization processcomprises:

-   -   (A) contacting at least one olefin monomer with at least one        precision fragmentation assemblage catalyst;    -   (B) polymerizing said olefin monomer to produce a polyolefin;    -   (C) isolating said polyolefin,        -   wherein said catalyst comprises:            -   (i) a precision fragmentation assemblage; and            -   (ii) at least one catalytic component;            -   wherein said precision fragmentation assemblage                comprises:                -   (a) a plurality of fragmentation domains; and                -   (b) one or more fragmentation zones;                -   wherein said fragmentation domain comprises at least                    one first polymer; and                -   wherein said fragmentation zone comprises at least                    one connecting phase, said connecting phase                    comprising at least one second polymer.

Used herein, the following terms have these definitions:

The term “(meth)acryl” refers to both “acryl” and “methacryl”. Forexample, “methyl (meth)acrylate” refers to both “methyl acrylate” and“methyl methacrylate”.

A “fragmentation domain” is a domain that includes one or more polymericchains of a “first polymer” prepared from at least one “first monomer”,and can be combined with other fragmentation domains to form a largerassemblage defined herein as a “precision fragmentation assemblage”(“PFA”). Each fragmentation domain is itself a particle, which isincorporated into a larger PFA particle. The chains of first polymermay, optionally, bear one or more “tether groups”.

A “precision fragmentation assemblage” (“PFA”) is an assemblage of atleast one type of plural fragmentation domains. The interstitial regionwhich exists among those fragmentation domains is a “fragmentationzone”. A fragmentation zone includes at least one “connecting phase” andmay, optionally, include one or more pore phases. The connecting phaseconnects the individual fragmentation domains so that they do not detachfrom the PFA during its preparation, during the preparation of the PFAcatalyst, or from the growing polyolefin particle during olefinpolymerization utilizing the PFA catalyst.

The “connecting phase” includes at least one “second polymer” which mayor may not have the same composition as the “first polymer” of thefragmentation domain. The “second polymer” is prepared from one or more“second monomer”.

An optional “pore phase” may be filled with one or more substances insolid, liquid, gaseous, or supercritical state. One function of the“pore phase” is to facilitate movement of substances from the outersurface of the PFA to interior surfaces of the PFA. The pore phase istypically prepared by polymerizing second monomer in the presence of a“porogen”, in which it is soluble, to produce second polymer which isinsoluble in the porogen. The process is referred to as “polymerizationinduced phase separation” (“PIPS”).

A PFA can be loaded with a “component” such as transition metal atoms,ligands associated with those transition metal atoms, and, optionally,an “activator component” such as aluminum alkyls, aluminoxanes, andborates to produce a “precision fragmentation assemblage catalyst” (“PFAcatalyst”). PFA catalysts can be used to catalyze polymerization ofolefins. As such, each PFA catalyst particle acts as a template for alarger bulk particle of polyolefin that forms during polymerization. Theterm “PFA” refers to a “precision fragmentation assemblage” as it existsbefore loading with transition metal atoms, ligands associated with thetransition metal atoms, and, optionally, activators. The term “PFAcatalyst” refers to the PFA after such loading. The “PFA” structureserves as a template for well-controlled precision fragmentation duringpolymerization. A “PFA catalyst” can be used to provide well-controlledprecision fragmentation during olefin polymerization. In this way,fragmentation domains of predetermined size and shape move away from oneanother to maximize olefin polymerization efficiency while avoidingactual physical detachment from the larger PFA catalyst particle, ofwhich it is a part, as that PFA catalyst particle becomes an even largerpolyolefin particle.

A “fragmentation zone” is, by design, a zone of relative weakness and/orflexibility in a precision fragmentation assemblage. The fragmentationzone includes the interstitial region among the fragmentation domainscontained within the PFA. It is not a requirement of the presentinvention that the surfaces of adjacent fragmentation domains touch, butwhen they do touch the interface at the point of contact between theadjacent fragmentation domains may be considered to be part of thefragmentation zone. It is a requirement of the present invention thatthe fragmentation zone include at least one “connecting phase” and thateach connecting phase include at least one “second polymer” which may,optionally, bear one or more “tether groups”. The fragmentation zone mayfurther, optionally, include one or more pore phases, one or more typesof plural polymeric nanoparticles (“PNPs”), or combinations thereof.Appropriate selection of fragmentation zone size, composition, porosity,morphology, and degree of uniformity may be accomplished to affordprecise control of PFA fragmentation rate and fragmentation pattern.

A “tether group” is a functional group covalently bound to a polymerchain, and capable of interacting with some portion of a catalyticcomponent (e.g., a transition metal atom, or some moiety that is part ofa transition metal complex), or some moiety that is part of an activatorcomponent (e.g., of an aluminum alkyl, an aluminoxane, or a boron basedactivator). A “tether group” may interact with these moieties byσ-bonding, π-bonding, ionic association, polar interaction, covalentbonding, or a combination thereof. A “tether group” may be covalentlybound to chains of first polymer, of second polymer, of optionalpolymeric nanoparticle, or combinations thereof.

“Polymeric nanoparticles” (“PNPs”) are any crosslinked polymericparticles having an average particle size, in microns, of 0.002 to 0.1,preferably 0.002 to 0.05, more preferably 0.002 to 0.02, and mostpreferably 0.005 to 0.01.

A “PNP-PFA” is a precision fragmentation assemblage that furtherincludes plural polymeric nanoparticles. The fragmentation zone of aPNP-PFA includes PNPs. The PNPs may be covalently or otherwise bound tothe PFA, or may be physically entrapped within the PFA. When covalentlybound to the PFA, PNPs may be bound to the second polymer, to thefragmentation domain, to each other, or any combination of these.

“Fragmentation” is the process by which a “fragmentation domain”separates from adjacent fragmentation domains of a catalytic PFA. It isdesirable that fragmentation of catalytic PFAs occur in a preciselycontrolled manner during olefin polymerization. In a preferredembodiment, the fragmentation domains move away from each other but donot detach from the PFA.

A “pendant” group is a group that is attached to the backbone of apolymer. The term pendant may be used to describe a group that isactually part of a polymerized monomer unit. For example, thehydroxyethyl group of a polymerized unit of 2-hydroxyethyl methacrylatemay be referred to as a “pendant hydroxyethyl group”, or more generallyas “pendant hydroxy functionality”. It is also common to refer to largegroups attached to a polymer backbone as “pendant” when those largegroups are compositionally distinct from the backbone polymer. A“pendant” group may further be described as “pendant to” the backbone.

A “terminal” group resides at the end of a polymer chain and ischemically attached to a terminal, polymerized, monomer unit. A terminalgroup may, for example, have a composition distinct from the compositionof the backbone of the polymer. A “pendant” group may occur in a“terminal” position. As such, a “terminal” group is a special case of a“pendant” group.

A group may also be “internal” to a polymer backbone. For a functionalgroup to be an “internal group”, the actual functional portion must bepart of the backbone of the polymer.

A tether group may reside in a pendant, terminal, or internal positionof a chain of first polymer, second polymer, or polymeric nanoparticle.A tether group may be incorporated into a polymer chain as part of amonomer or, for example, by post-reaction of functional groups which arealready attached to the polymer chain.

“Tg” is the “glass transition temperature” of a polymeric phase. Theglass transition temperature of a polymer is the temperature at which apolymer transitions from a rigid, glassy state at temperatures below Tgto a fluid or rubbery state at temperatures above Tg. The Tg of apolymer is typically measured by differential scanning calorimetry (DSC)using the mid-point in the heat flow versus temperature transition asthe Tg value. A typical heating rate for the DSC measurement is 20Centigrade degrees per minute. The Tg of various homopolymers may befound, for example, in Polymer Handbook, edited by J. Brandrup and E. H.Immergut, Interscience Publishers. The Tg of a polymer is estimated byusing the Fox equation (T. G. Fox, Bull. Am. Physics Soc., Volume 1,Issue No. 3, page 123 (1956)).

“Effective Tg”. When a substance having some degree of solubility in apolymer is imbibed by that polymer, the softening temperature of thepolymer decreases. This plasticization of the polymer can becharacterized by measuring the “effective Tg” of the polymer, whichtypically bears an inverse relationship to the amount of solvent orother substance contained in the polymer. The “effective Tg” of apolymer containing a known amount of a substance dissolved within ismeasured just as described above for “Tg”. Alternatively, the “effectiveTg” may be estimated by using the Fox equation (supra), assuming a valuefor Tg (e.g., the freezing point) of the solvent or other substancecontained in the polymer.

Molecular Weight. Synthetic polymers are almost always a mixture ofchains varying in molecular weight, i.e., there is a “molecular weightdistribution”, abbreviated “MWD”. For a homopolymer, members of thedistribution differ in the number of monomer units which they contain.This way of describing a distribution of polymer chains also extends tocopolymers. Given that there is a distribution of molecular weights, themost complete characterization of the molecular weight of a given sampleis the determination of the entire molecular weight distribution. Thischaracterization is obtained by separating the members of thedistribution and then quantitating the amount of each that is present.Once this distribution is in hand, there are several summary statistics,or moments, which can be generated from it to characterize the molecularweight of the polymer.

The two most common moments of the distribution are the “weight averagemolecular weight”, “M_(w)”, and the “number average molecular weight”,“M_(n)”. These are defined as follows:M_(w)=Σ(W_(i)M_(i))/ΣW_(i)=Σ(N_(i)M_(i) ²)/ΣN_(i)M_(i)M_(n)=ΣW_(i)/Σ(W_(i)/M_(i))=Σ(N_(i)M_(i))/ΣN_(i)where:

M_(i)=molar mass of i^(th) component of distribution

W_(i)=weight of i^(th) component of distribution

N_(i)=number of chains of i^(th) component

and the summations are over all the components in the distribution.M_(w) and M_(n) are typically computed from the MWD as measured by GelPermeation Chromatography (see the Experimental Section).

“Particle size” is the diameter of a particle. The “average particlesize” determined for a collection of particles (e.g., fragmentationdomains) is the “weight average particle size”, “d_(w)”, as measured byCapillary Hydrodynamic Fractionation technique using a Matec CHDF 2000particle size analyzer equipped with a HPLC type Ultra-violet detector.

The term “particle size distribution” and the acronym “PSD” are usedinterchangeably herein. “Polydispersity” is used in the art as a measureof the breadth of the PSD. Used herein, “polydispersity” is adescription of the distribution of particle sizes for a plurality ofparticles. As such, “polydispersity” and “PSD polydispersity” are usedinterchangeably. PSD polydispersity is calculated from the weightaverage particle size, d_(w), and the number average particle size,d_(n), according to the formulae:PSD Polydispersity=(d _(w))/(d _(n)),whered_(n)=Σn_(i)d_(i)/Σn_(i)d_(w)=Σn_(i)d_(i)d_(i)/Σn_(i)d_(i)andwhere n_(i) is the number of particles having the particle size d_(i).

Estimation of whether a polymer and another component (e.g., anotherpolymer or low molecular weight substance) will be miscible may be madeaccording to the well-known methods delineated in D. W. Van Krevelen,Properties of Polymers, 3rd Edition, Elsevier, pp. 189–225, 1990. Forexample, Van Krevelen defines the total solubility parameter (δ_(t)) fora substance by:δ_(t) ²=δ_(d) ²+δ_(p) ²+δ_(h) ²,

where δ_(d), δ_(p), and δ_(h) are the dispersive, polar, and hydrogenbonding components of the solubility parameter, respectively. Values forδ_(d), δ_(p), and δ_(h) have been determined for many solvents,polymers, and polymer segments, and can be estimated using the groupcontribution methods of Van Krevelen. For example, to estimate whether apolymer having a given composition will be miscible with a particularsolvent, one calculates δ_(t) ² for the polymer and δ_(t) ² for thesolvent. Typically, if the difference between the two, Δδ_(t) ², isgreater than 25 (i.e., Δδ_(t)>5), then the polymer and the solvent willnot be miscible. These calculations are particularly useful fordetermining if a particular solvent will act as a porogen during thepolymerization of monomers which are soluble in that solvent. In suchcase, it is desirable for the polymer thus formed to precipitate fromthe solvent during or after polymerization.

If, instead, it is desired to determine whether two polymers, differingin composition, will be miscible, the same calculations may be carriedout, but the predicted upper limit of Δδ_(t) ² for miscibility willdecrease as the molecular weight of one or both of polymers underconsideration increases. This decrease is thought to parallel thedecrease in entropy of mixing which occurs as the molecular weight ofthe components being mixed increases. For example, two polymers, eachhaving a degree of polymerization of 100, will likely be immiscible evenif the value of Δδ_(t) ² for their mixture is 9, or even 4 (i.e.,Δδ_(t)=3, or even 2). Still higher molecular weight polymers may beimmiscible at even lower values of Δδ_(t). Other sources of miscibilityinformation include Olabisi et al., Polymer-Polymer Miscibility,Academic Press, NY, 1979; Coleman et al., Specific Interactions and theMiscibility of Polymer Blends, Technomic, 1991; and A. F. M. Barton, CRCHandbook of Solubility Parameters and Other Cohesion Parameters, 2^(nd)Ed., CRC Press, 1991.

The fragmentation domains useful in the present invention may beprepared by any appropriate method known to the art, including, but notlimited to, emulsion polymerization, suspension polymerization,microemulsion polymerization, slurry polymerization, solutionpolymerization, polymerization induced phase separation, thermallyinduced phase separation, and solvent induced phase separation.Descriptions of these methods are disclosed in Blackley, D. C. EmulsionPolymerisation; Applied Science Publishers: London, 1975; Odian, G.Principles of Polymerization; John Wiley & Sons: New York, 1991;Emulsion Polymerization of Acrylic Monomers; Rohm and Haas, 1967. Whenthe average particle size of the fragmentation domain is in the range0.8 microns to 20 microns, the preferred method of polymerization isaqueous suspension polymerization. When the average particle size of thefragmentation domain is in the range 0.04 microns to less than 0.8microns, the preferred polymerization is aqueous emulsionpolymerization. If it is desired to prepare fragmentation domains in thesize range 0.02 microns to less than 0.04 microns, it is preferred touse microemulsion techniques to prepare them. It is preferred to preparefragmentation domains of size 0.002 microns to less than 0.02 microns bysolution techniques and polymerization induced phase separationtechniques useful for preparation of polymeric nanoparticles (PNPs).Typically, the average particle size of a fragmentation domain is 0.002micron to 20 microns, preferably 0.002 micron to 10 microns, morepreferably 0.1 micron to 5 microns, and most preferably 0.5 micron to 3microns. These ranges, and all others used herein, are inclusive andcombinable. The polydispersity of the PSD of plural particles of a givenfragmentation domain is typically 1.000, i.e., monodisperse, to 5,preferably 1.000 to 1, more preferably 1.000 to 1.3, and most preferably1.000 to 1.1. A particularly preferred embodiment is one in which theplural particles of a given fragmentation domain are monodisperse, thatis, they exhibit a polydispersity of unity. Two or more sizes offragmentation domain may be combined by mixing, or may be prepared insitu, using techniques well known in the art to form multimodalfragmentation domain particle size distribution. Fragmentation domainsdiffering in composition and/or morphology may also be combined in theseways. For example, a fragmentation domain bearing one type of tethergroup could be combined with a fragmentation domain bearing another typeof tether group.

The fragmentation domains useful in the present invention must includeat least one first polymer, which may be a homopolymer or a copolymerformed from at least one first monomer, a non-exhaustive list of whichis given herein. Although the first polymer may be any polymer orcopolymer made by any means, addition polymers and condensation polymersare particularly useful and are preferred. Of those two types ofpolymers, addition polymers are particularly preferred. The firstmonomers from which the addition polymer is formed are free-radicalpolymerizable ethylenically-unsaturated monomers. Examples ofmono-ethylenically unsaturated monomers include: C₁–C₃₀ linear orbranched chain alkyl (meth)acrylates, bornyl (meth)acrylate, andisobornyl (meth)acrylate; styrene, substituted styrenes; butadiene;monomers containing α,β-unsaturated carbonyl functional groups such asfumarate, maleate, cinnamate and crotonate; (meth)acrylonitrile; andcombinations thereof. A non-limiting list of halogen containing firstmonomers includes 2-bromoethyl acrylate, 2-bromoethyl methacrylate,4-bromostyrene, vinylidene chloride, vinyl chloride, pentafluorophenylacrylate, pentafluorophenyl methacrylate, 2-(perfluoroalkyl)ethyl(meth)acrylates, 2-(perfluorododecyl)ethyl acrylate,2-(perfluorododecyl)ethyl methacrylate, 2-(perfluorohexyl)ethylacrylate, 2-(perfluorohexyl)ethyl methacrylate, and vinylidene fluoride.The first monomer of the present invention may, further, be a siloxaneor silane monomer, with ethylenically unsaturated siloxane monomersbeing particularly preferred silicon containing monomers. Siliconcontaining monomers useful in the present invention include: divinylsilane, trivinyl silane, dimethyl divinyl silane, divinyl methyl silane,methyl trivinyl silane, diphenyl divinyl silane, divinyl phenyl silane,trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyl silane,dimethyl vinyl disiloxane, poly(methyl vinyl siloxane), poly(vinyl hydrosiloxane), poly(phenyl vinyl siloxane), and mixtures thereof.

Formation of the first polymer of the present invention mayalternatively be achieved by condensation polymerization. Typically, acondensation polymer is formed as the product of reaction between twodistinct multifunctional first monomers, each having reactive groupsreactive with reactive groups on the other. An example of such areactive pair is paraphenylene diisocyanate and hexamethylene diamine.Crosslinking may be achieved by incorporating, for example,trifunctional monomers such as diethylene triamine. Other suitablemonomers and methods for preparing condensation polymers therefrom canbe found in U.S. Pat. Nos. 4,360,376 and 3,577,515.

The first polymer may, optionally, include one or more tether groups. Atether group may be any group capable of interaction with the catalyticcomponent, the activator component, or both. Functional groups capableof such interaction as part of a tether group include, but are notlimited to, epoxy, vinyl, allyl, primary amino, secondary amino, imino,amide, imide, aziridinyl, hydrazide, amidino, hydroxy, hydroperoxy,carboxyl, formyl, methoxycarbonyl, carbamoyl, sulfone (SO₂), sulfine(SO), sulfeno (S), thiol, thiocarboxyl, thioformyl, pyrrolyl,imidazolyl, piperidyl, indazolyl and carbazolyl.

Examples of mono-ethylenically unsaturated monomers suitable as firstmonomers and having these functional groups include, but are not limitedto: alcohols including hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate; vinyl esters including vinyl acetate and acetoxystyrene;epoxides including glycidyl (meth)acrylate; amines includingN-butylaminoethyl (meth)acrylate, N,N-di(methyl)aminoethyl(meth)acrylate; and (meth)acrylamide and substituted (meth)acrylamides.

Examples of multi-ethylenically unsaturated monomers include butadiene,1,4-butanediol di(meth)acrylate, 1,1,1-trimethylolpropanetri(meth)acrylate, allyl (meth)acrylate, divinylbenzene,trivinylbenzene, divinyltoluene, divinylketone, diallyl phthalate,diallyl maleate, N,N′-methylene bisacrylamide, ethyleneglycoldi(meth)acrylate and polyethyleneglycol di(meth)acrylate. Flourinatedmulti-ethylenically unsaturated monomer are also useful as firstmonomer. For example, fluorinated diacrylates having structure1,3-[CH2:CHCO2CH2CHOHCH2OC(CF3)2]2C6H3Rf, where Rf=C1–C30 perfluoroalkylas disclosed in U.S. Pat. No. 4,914,171. Polymers derived frommulti-ethylenically unsaturated monomers, which also serve ascrosslinking monomers, typically bear residual ethylenic unsaturation(e.g., vinyl groups and allyl groups) as the result of incompletereaction. Although the functional groups useful in the present inventionare usually contained in polymer chains as pendant tether groups, orportions of pendant tether groups, the functional groups may in somecases be part of the backbone of the polymer. For example, acarbon-carbon double bond present in the backbone of the first polymer,as the result of 1,4-addition of butadiene, would be such a functionalgroup.

The level of multi-ethylenically unsaturated monomer, present aspolymerized units, in the first polymer is typically 0.5 weight percentto 100 weight percent, preferably 2 weight % to 100 weight %, morepreferably 10 to 80 weight %, and most preferably 20 to 60 weight %,based on the weight of first polymer. The level of mono-ethylenicallyunsaturated monomer, present as polymerized units, in the first polymeris typically 0 weight percent to 99.5 weight percent, preferably, 0weight % to 98 weight %, more preferably 20 to 90 weight %, and mostpreferably 40 to 80 weight %, based on the weight of first polymer.

The fragmentation domain may include a single phase, or multiple phases.When multiple phases are present, at least one phase will contain afirst polymer. Other phases may include, for example: other firstpolymer of a different composition; non-polymers in solid, liquid,gaseous, or super-critical state; and combinations thereof. A pore phasemay be a vacuum, or may contain air, or other gases, or combinationsthereof. The fragmentation domain may have any shape. For example, thefragmentation domain may be spherical, elliptical, or hemispherical. Anespecially preferred shape is spherical. Fragmentation domains whichinclude more than one phase many have any morphology, including, forexample: core/shell wherein the shell is continuous and unbroken;core/shell wherein the shell has a single hole; and core/shell whereinthe shell has multiple holes or pores. Examples of how multiple phasefragmentation domains can be prepared are disclosed in U.S. Pat. Nos.5,835,174, 5,976,405, 6,037,058, 6,271,898, and 5,972,363, and in patentpublications EP-0915147, US-2002-0110690, and EP-2002-256005.

One skilled in the art will recognize that, when aqueous emulsionpolymerization and microemulsion polymerization are used to prepare thefirst polymer of the present invention, surfactants and initiators willbe present in the reaction medium. Conventional surfactants may be usedto stabilize the emulsion polymerization systems before, during, andafter polymerization of monomers. For emulsion polymers, theseconventional surfactants will usually be present at levels of 0.1percent to 6 percent by weight based on the weight of total monomer,whereas microemulsion polymerizations my require level as high as 30weight %. Useful surfactants include: anionic surfactants, for example,sodium lauryl sulfate and sodium dodecyl benzene sulfonate; nonionicsurfactants, for example, glycerol aliphatic esters and polyoxyethylenealiphatic esters; and amphoteric surfactants, for example,aminocarboxylic acids, imidazoline derivatives, and betaines.

Initiation of emulsion polymerization may be carried out by the thermaldecomposition of free radical precursors, also called initiators herein,which are capable of generating radicals suitable for initiatingaddition polymerization. Suitable thermal initiators such as, forexample, inorganic hydroperoxides, inorganic peroxides, organichydroperoxides, and organic peroxides, are useful at levels of from 0.05percent to 5.0 percent by weight, based on the weight of monomers. Freeradical initiators known in the art of aqueous emulsion polymerizationand micro-emulsion polymerization include water-soluble free radicalinitiators, such as hydrogen peroxide, tert-butyl peroxide, benzoylperoxide, t-butyl peroctoate; alkali metal (sodium, potassium orlithium) or ammonium persulfate; azo initiators such asazobisisobutyronitrile or 2,2′-azobis(2-amidinopropane) dihydrochloride;or mixtures thereof. Such initiators may also be combined with reducingagents to form a redox system. Useful reducing agents include sulfitessuch as alkali metal meta bisulfite, or hyposulfite, sodium thiosulfate,or isoascorbic acid, or sodium formaldehyde sulfoxylate. The freeradical precursor and reducing agent together, referred to as a redoxsystem herein, may be used at a level of from about 0.01% to 5%, basedon the weight of monomers used. Examples of redox systems include:t-butyl hydroperoxide/sodium formaldehyde sulfoxylate/Fe(III); t-butylhydroperoxide/isoascorbic acid/Fe(III); and ammonium persulfate/sodiumbisulfite/sodium hydrosulfite/Fe(III). The polymerization temperaturemay be 10° C. to 110° C., depending upon such things as free radicalinitiator decomposition constant and reaction vessel pressurecapabilities.

Although a chain transfer agent such as a mercaptan (for example:n-octyl mercaptan, n-dodecyl mercaptan, butyl or methylmercaptopropionate, mercaptopropionic acid at 0.05 to 6% by weight,based on total weight of monomer) may be employed to limit the formationof any significant gel fraction or to control molecular weight inemulsion polymerization, it is generally preferred to maintain the gelfraction, the level of crosslinking, of the fragmentation domain at ahigh level, so chain transfer agents are commonly not employed, or areused at a low level, typically less than 1.0 percent by weight, based ontotal monomer weight.

When the first polymer of the fragmentation domain is formed by aqueoussuspension polymerization, the initiators listed for emulsionpolymerization supra may be used. Stabilization of fragmentation domainsformed by suspension polymerization (i.e., those particles having a sizeof greater than approximately 0.8 microns to 20 microns or more) isconveniently accomplish using water soluble polymers including polyvinylalcohol, poly-N-vinyl pyrrolidone, carboxymethylcellulose, gelatin,hydroxyethylcellulose, partially saponified polyvinyl acetate,polyacrylamide, polyethylene oxide, polyethyleneimine, polyvinylalkylethers, polyacrylic acid copolymers of polyacrylic acid, polyethyleneglycol, sodium polystrenesulfonate.

In another preferred embodiment of the present invention, a“macromolecular organic compound” having a hydrophobic cavity is presentin the polymerization medium used to form the fragmentation domain.Preferably, the macromolecular organic compound is used when it isnecessary to transport ethylenically unsaturated monomers, or othermolecules which are not monomers, having very low water solubility.Examples of monomers having very low water solutility include lauryl orstearyl (meth)acrylates. By “very low water solubility” it is meant awater solubility at 25° C. to 50° C. of no greater than 50millimoles/liter. For example, the macromolecular organic compound maybe added to the monomer composition, the macromonomer aqueous emulsion,or the polymerization reaction mixture used to form the aqueouscopolymer composition. Suitable techniques for using a macromolecularorganic compound having a hydrophobic cavity are disclosed in, forexample, U.S. Pat. Nos. 5,521,266 and 6,037,058.

A “precision fragmentation assemblage” (“PFA”) is an assemblage of“fragmentation domains”, the interstitial space among which is the“fragmentation zone” which, in turn, includes at least one “connectingphase” and, optionally, one or more “pore phases”. Typically, the ratioof the total volume of the fragmentation zone to the total volume of thefragmenation domains contained within a PFA is 0.10 to 10, preferably0.20 to 2.0, more preferably 0.30 to 1.0, and most preferably 0.3 to0.5.

The connecting phase connects the individual fragmentation domains sothat they do not detach from the PFA during its preparation, thepreparation of the PFA catalyst, or the olefin polymerization utilizingthe PFA catalyst. The “connecting phase” includes at least one “secondpolymer” which may or may not have the same composition as the “firstpolymer” of the fragmentation domain. Any of the first monomers listedsupra as useful for preparation of the “first polymer” are also usefulas second monomers for preparation of the second polymer. Typically, theratio of the total weight of second polymer to the total weight of firstpolymer is 0.005 to 10, preferably 0.01 to 1.0, more preferably 0.05 to0.5, and most preferably 0.1 to 0.20. The level of multi-ethylenicallyunsaturated second monomer, present as polymerized units, in the secondpolymer is typically 0.1 weight percent to 100 weight percent,preferably 0.5 weight % to 50 weight %, more preferably 1.0 to 20 weight%, and most preferably 2.0 to 10 weight %, based on the weight of secondpolymer. The level of mono-ethylenically unsaturated monomer, present aspolymerized units, in the second polymer is typically 0 weight percentto 99.9 weight percent, preferably, 50 weight % to 99.5 weight %, morepreferably 80 to 99 weight %, and most preferably 90 to 98 weight %,based on the weight of second polymer. Chain transfer agents, such asthose listed supra may be used to regulate the length of the chains ofsecond polymer, thereby precisely controlling the strength andflexibility of the connecting phase when used in concert with otherparameters such as, for example, composition.

The optional “pore phase” may be filled with one or more substances insolid, liquid, gaseous, or supercritical state. Though not wishing to bebound be any particular theory, it is thought that, when a pore phase ispresent, that pore phase facilitates movement of substances such assolvent, catalytic components, activator components, and olefin monomersfrom the outer surface of the PFA to interior surfaces of the PFA.Although morphologies useful in the PFA of the present invention existin which the individual pores of the pore phase do not interconnect, orin which there is no pore phase, it is preferred that there be a porephase and that at least a portion of those individual pores dointerconnect such that paths exist for transfer of solvents, catalyticcomponents, activator components, and other substances between theexterior of the PFA and its interior. More preferably, most or all ofthe pores interconnec. Most preferably, the pore phase and connectingphase are co-continuous (i.e., bicontinuous, or even multicontinuous ifthere is more than one type of connecting phase and/or more than type ofone pore phase). Typically, the pore volume of the PFA per dry weight ofthe PFA, expressed in cc/g, is 0.1 to 9.0, preferably 0.30 to 4.0, morepreferably 0.5 to 3.0, and most preferably 1.0 to 2.5. The average poresize, in microns, is typically 0.005 to 10, preferably 0.01 to 2.0, morepreferably 0.02 to 1.0, and most preferably 0.02 to 0.50. The percent oftotal pore volume deriving from pores of size less than 0.050 micronsfor all pores having a pore size of 0.005 to 10 microns is typically 20to 95, preferably 30 to 80, more preferably 40 to 70, and mostpreferably greater than 50 to 60. The ratio of the volume of the porephase to the volume of the connecting phase is typically 0.10 to 100,preferably 0.50 to 10, more preferably 1.0 to 5.0, and most preferably2.0 to 5.0.

When a pore phase is not present in the fragmentation zone of the PFA ofthe present invention, it is preferred that the degree of crosslinkingof the second polymer be such that the second polymer will swellsufficiently with solutions bearing the catalytic component and theactivator component during catalyst loading that those components canpenetrate to the interior of the PFA. The same is true for penetrationof olefin monomer during olefin polymerization catalyzed by the PFAcatalyst. Therefore, when no pore phase is present in the fragmentationzone, it is preferred that the level of multi-ethylenically unsaturatedmonomer, present as polymerized units, in the second polymer is 0.05weight percent to 10 weight percent, more preferably 0.1 weight % to 5weight %, and most preferably 0.2 to 1 weight %, based on the weight ofsecond polymer. Further, when no pore phase is present in thefragmentation zone, it is preferred that the level of mono-ethylenicallyunsaturated monomer, present as polymerized units, in the second polymeris 90 weight percent to 99.95 weight percent, more preferably 95 to 99.9weight %, and most preferably 99 to 99.8 weight %, based on the weightof second polymer. It is well known in the art that many monomers (e.g.,butyl acrylate) undergo self crosslinking. When such monomers arepresent, it may be possible to reduce the level of multi-ethylenicallyunsaturated monomer, and in some cases eliminate there use altogether toachieve a desired level of crosslinking.

The fragmentation zone of the PFA of the present invention may,optionally, contain “polymeric nanoparticles”, PNPs. Such PNP bearingPFAs, may alternatively be referred to as “PNP-PFAs”. The PNPs useful inthe present invention may be prepared using as third monomer any of themonomers and types of monomer disclosed herein as being first monomerssuitable for preparation of the first polymer. Although the compositionof a PNP may be identical to that of the first polymer, the secondpolymer, or both, its composition may vary widely from either or both.The level of multi-ethylenically unsaturated monomer, present aspolymerized units, in the PNP is typically 2 weight percent to 100weight percent, preferably 5 weight % to 100 weight %, more preferably10 to 80 weight %, and most preferably 20 to 60 weight %, based on theweight of PNP. The level of mono-ethylenically unsaturated monomer,present as polymerized units, in the PNP is typically 0 weight percentto 98 weight percent, preferably, 0 weight % to 95 weight %, morepreferably 20 to 90 weight %, and most preferably 40 to 80 weight %,based on the weight of PNP. The PNPs are crosslinked polymers having anaverage particle size, in microns, of typically 0.002 to 0.1, preferably0.002 to 0.05, more preferably 0.002 to 0.02, and most preferably 0.005to 0.01. The polydispersity of the PSD of the PNPs is typically 1.00 to5.0, preferably 1.00 to 3.0, more preferably 1.00 to 1.5, and mostpreferably 1.00 to 1.3. It is desirable that, when plural PNPs arepresent in a PFA, the plural PNPs remain distributed within the PFA,without detaching from the PFA, throughout loading with catalyticcomponent and optional activator component, and throughout subsequentolefin polymerization. This attachment may be accomplished by any means,including covalent bonding, ionic association, and polar interaction, orcombinations thereof, of the PNP to second polymer, to fragmentationdomain, to other PNPs, or combinations thereof. Physical entrapment ofthe PNPs within the PFA may also be utilized.

Although PNPs useful in the present invention may be devoid offunctionality suitable for causing attachment of the PNP to PFAstructures (e.g., fragmentation domains, connecting phases, and otherPNPs) during formation of the PFA, it is preferred that the PNPs usefulin the present invention bear at least one such “attachment group”capable of providing such attachment. Preferred attachment groupsinclude functional groups useful in providing attachment of monomerunits to growing polymer chains during free radical and condensationpolymerization. The attachment groups useful for participation in freeradical polymerization may, for example, be vinyl groups and allylgroups. The attachment groups useful for participation in condensationpolymerization are moieties such as amine and isocyanate enumeratedsupra. More preferably, the attachment groups are free radicalpolymerizable ethylenically unsaturated groups. When PNPs bearing two ormore such attachment groups are present during polymerization of themonomers to form the second polymer, it may not be necessary thatmulti-ethylenically unsaturated monomer, or other multi-functionalmonomer, be present, or that less may be required. In that case the PNPitself may provide the necessary degree of crosslinking for the secondpolymer. However, it is generally preferred, even in this case, that theranges of level multi-ethylenically unsaturated monomer, or otherappropriate multi-functional monomer, used to prepare the second polymerbe the same as those stated supra.

The PNPs of the present invention typically have an “apparent weightaverage molecular weight” in the range of 5,000 to 1,000,000, preferablyin the range of 10,000 to 500,000 and more preferably in the range of15,000 to 100,000. As used herein, “apparent weight average molecularweight” reflects the size of the PNP particles using standard gelpermeation chromatography methods, e.g., using THF solvent at 40° C., 3Plgel™ Columns (Polymer Labs, Amherst, Mass.), 100 Angstrom (10 nm), 10³Angstroms (100 nm), 10⁴ Angstroms (1 micron), 30 cm long, 7.8 mm ID, 1milliliter per minute, 100 microliter injection volume, calibrated tonarrow polystyrene standards using Polymer Labs CALIBRE™ software.

Polymeric nanoparticles useful in the present invention can be preparedby an means known in the art to provide PNPs having the characteristicsdescribed supra. Methods for preparing PNPs are disclosed in thesepublications: EP-2002-1245587, EP-2002-1245644, US-2002-0193521, andUS-2002-0177522.

It is preferred that the PFA useful in the present invention is preparedby agglomerating fragmentation domains. Either concurrent with, orsubsequent to the step of agglomerating the fragmentation domains, thefollowing additional components are added to the agglomerated particles:at least one second monomer to be polymerized to form the secondpolymer; optionally, one or more porogens; optionally, a plurality ofPNPs; and initiator. Alternatively, the second polymer can be acondensation polymer. In such case, and initiator is not required. Theagglomeration may be achieved by any means know to the art. Preferredmethods of agglomeration include spray drying, coagulation, jetting, andcombinations thereof. More preferably, the agglomeration method is amethod selected from the group consisting of coagulation, jetting, andcombinations thereof. The most preferred agglomeration method iscoagulation. Once formed, the agglomerate particles, including monomer,initiator, and optional components are subjected to conditions suitableto cause polymerization of the monomers to form second polymer. If aporogen is present during the polymerization, that porogen should bechosen (see the methods of van Krevelen supra) so that the secondmonomers are soluble in the porogen, yet the second polymer willseparate from the porogen during or after polymerization to occupy apore phase. A preferred method of agglomeration is coagulation. In apreferred embodiment, an aqueous emulsion containing a plurality offragmentation domains is combined with a aqueous emulsified monomermixture from which the second polymer will be made. The droplet size ofthe monomer droplets, which optionally contain porogen, is typicallyless than 10 microns, and preferably 1 micron or less. The monomerdroplets and the fragmentation domains are then destabilized by, forexample, adding multivalent cations to the combined aqueous system.Examples of substances useful in causing destabilization and coagulationof fragmentation domains and emulsion droplets include, but are notlimited to: sodium chloride, potassium chloride, sodium sulphate,ammonium chloride, calcium chloride, magnesium chloride, magnesiumsulphate, barium chloride, ferrous chloride, aluminum sulphate,potassium alum, iron alum, hydrochloric acid, sulphuric acid, phosphoricacid and acetic acid. Particularly useful cations are Mg²⁺ and Ca²⁺.Because spherical particles having narrow particle size distributionsmay be desirable in the PFA, the PFA catalyst, and the polyolefinproduct, the well-known methods of particle classification can be usedto narrow the PSD of the PFA particles. Classification can, for example,be achieved by screening plural PFA particles, keeping desired particlesize fractions. A more preferred method of achieving narrow PSD and morespherical agglomerated particles is to carry out a “spheroidcoagulation” as disclosed in U.S. Pat. Nos. 4,401,806, 4,897,462,5,514,772, and 4,277,426. Another preferred method of achieving narrowPSD is through “jetting” as disclosed in U.S. Pat. No. 3,922,255. Ifdesired, the PSD of PFA particles prepared by spheroid coagulation maybe even further narrowed through additional classification. When spraydrying is utilized in the formation of PFAs, an aqueous system includingplural fragmentation domains, monomer, and optional porogen may be spraydried, with polymerization occurring during or after isolation, or thefragmentation domains may first be isolated as agglomerates by spraydrying and then infused with monomer and optional porogen, andpolymerized.

In a further embodiment of the present invention, it is desirable thatthe precision fragmentation assemblage have a structure wherein there isa core of fragmentation domains surrounded by one or more layers offragmentation domains of a different type. These differences in type offragmentation domain include, but are not limited to: composition,including functional group type and amount: particle size and PSD;particle morphology; and degree of crosslinking. Further, a specificfragmentation domain type may be utilized in more than one layer(including the core) in PFAs having two or more such regions, and theconcentration of that fragmentation domain may vary from layer to layer,or may be invariant. In these “layered PFAs”, the fragmentation zone forone layer may be identical to, or different from, other layers.Preparation of the fragmentation zone or zones may be accomplished, forexample, by a single polymerization of second monomer, and optionalporogen, after all fragmentation domain layers have been formed, orafter one or more layers of fragmentation domains have been formed. Forexample, a different type of fragmentation zone could be formed before,after or during formation of each layer of fragmentation domains, orbefore, during or after formation of only one or more of those layers,or any combination of thereof. Further, more than one type offragmentation domain may be present in the same layer, and layers mayinterpenetrate one another. A preferred method of producing layered PFAsis staged coagulation. For example, a first stage is formed bycoagulation of one or more types of fragmentation domain, and subsequentlayers are formed from subsequent coagulations of other fragmentationdomains. Although, any type of assemblage may be formed having regionsof different types or concentrations of fragmentation domain, includingregions containing no fragmentation domains, a preferred embodiment isone in which the regions are present concentrically about a core region.One or more layers of a layered PFA may have fragmentation zones free ofconnecting phase, provided that at least one layer does include aconnecting phase. It is particularly preferred that the outermost layerinclude a connecting phase.

Selection of, for example: amounts of second polymer, pore phase, andPNP relative to the amount of fragmentation domain; the Tg of the secondpolymer; and the degree of crosslinking of the second polymer willinfluence the ease and uniformity of loading the resulting PFA withcatalytic component, activator component, and any associated solvent,and the ease of penetration of the olefin monomer into the PFA catalyst.Moreover, these factors can be precisely manipulated to control theextent to which fragmentation domains are able to move away from eachother during olefin polymerization, and to control the localized strainwithin the PFA catalyst particle during olefin polymerization,particularly during the early stage (i.e., during consumption of thefirst 10 to 20 percent of the olefin monomer). Proper control of suchlocalized strain reduces the stress within the PFA catalyst particleduring olefin polymerization, minimizing, or eliminating detachment ofportions of that particle to form separate, smaller particles.Elimination of such gross and uncontrolled detachment is to be avoidedbecause it results in reactor fouling and shutdown, in reduction of theaverage particle size of the polyolefin product, and in a skewing andbroadening of the polyolefin PSD. Other factors affording precisecontrol of olefin polymerization are the amount, type, and location oftether groups. A tether group may be attached to a fragmentation domain,a second polymer, a PNP, or combinations thereof. Multiple types oftether group may be used in a PFA. In fact, multiple types of tethergroup may even be incorporated into the same chain of first polymer, orof second polymer, or of PNP. Further, when the fragmentation domainincludes more than one phase, different types of tether group may beplaced at different locations in the fragmentation domain. For example,if the fragmentation domain includes a polymeric shell surrounding avoid, it is possible to incorporate one type of tether group on theouter surface of the shell and another type on interior surface of theshell. In this way, the positioning of catalytic components andactivator components within the PFA can be precisely controlled, andmore than one type of catalytic environment may be formed within asingle PFA particle.

It is a further advantage of the present invention that the structure ofthe PFA may be constructed, for example, in a series of coagulationsteps wherein different types of fragmentation domain are layered ontothe PFA in successive coagulations. If desired, the amounts and types ofingredients used to produce the fragmentation zone may also be variedfrom one coagulation step to the next.

The PFAs of the present invention may be isolated from their aqueousdispersions or slurries as powders by well known methods including, forexample, spray drying, filtration and oven drying, freeze drying, anddevolatilizing extrusion. A preferred method is isolation of coagulatedPFA by filtration and fluid bed drying. The PFA can then be loaded withcatalytic component and, optionally activator component, typically in acarrier solvent such as an aliphatic or aromatic hydrocarbon, ormixtures thereof. It is even more preferred to prepare the PFA using aporogen that is the same as, or miscible with, the carrier solvent(e.g., aliphatic or aromatic hydrocarbon) for the catalytic componentand, optionally, the activator component. In this way the PFA may beloaded in situ to form the PFA catalyst, avoiding intermediate isolationsteps.

The average particle size, in microns, of the plural PFA particlesuseful in the present invention is typically 1 to 1000, preferably 10 to500, more preferably 20 to 100, and most preferably 40 to 70. Thepolydispersity of the PSD of the plural PFA particles is typically 1.0to 5.0, preferably 1.0 to 3.0, more preferably 1.0 to 1.5, and mostpreferably 1.0 to 1.3. The surface area of the PFA, in m²/g asdetermined by BET N₂ absorption, is typically 10 to 2000, preferably 50to 1000, more preferably 100 to 800, and most preferably 200 to 800. Thetotal amount of tether group attached to a PFA, given in mmoles oftether groups per gram of PFA, is typically 0.0 to 10, preferably 0.01to 5.0, more preferably 0.05 to 3.0, and most preferably 0.10 to 2.0.

Stock mixtures of the “PFA catalyst” of the present invention areprepared by combining the catalytic component, optionally the activatorcomponent, and the PFA of the present invention with an anhydroussolvent. Non-polar solvents such as aliphatic and aromatic hydrocarbonsare preferred. The combining of these materials is performed underanhydrous conditions using techniques well known in the art formanipulating air-sensitive materials. For example, the combining can beaccomplished by manipulation of the materials in a glovebox under dryArgon atmosphere. Any solvent: that can be dried; that does not reactwith or otherwise deleteriously interact with the catalytic component,the activator component, the PFA, or any combination thereof; and thatcan solubilized the catalyst and activator components at usefulconcentrations may be used as a solvent for the preparation of thecatalytic component, and for subsequent use in olefin polymerization.Aromatic hydrocarbons, alkyl substituted aromatic hydrocarbons, and C-4to C-20 alkanes are preferred. In a preferred embodiment of theformation of a stock solution of catalytic component and activatorcomponent, the solvent is anhydrous toluene. A catalytic component, forexample (BuCp)₂ZrCl₂ is combined with an activator solution, 10% MAOsolution in toluene. After 15 minutes, the solution turns a paleyellow-orange color. In a preferred embodiment of the preparation of thePFA catalyst, a slurry of plural PFA particles in dry toluene is shakenwhile adding a stock solution of catalytic component and activatorcomponent (for example, a solution of (BuCp)₂ZrCl₂/MAO in toluene). ThePFA particles become colored (yellow-orange in this example) while thesolution becomes clear and colorless or very light in color, indicatingthat the catalytic component has been absorbed into the PFA. The tolueneis removed under reduced pressure, and replaced with solvent (e.g., dryheptane). The slurry of PFA catalyst in solvent is transferred to apressure reactor which is then pressurized with dry Argon and olefinmonomer (see herein below) to begin the olefin polymerization. Althoughthe method of the preferred embodiment just described involves firstpreparing a solution of the catalytic component and the activatorcomponent in a solvent, and adding that solution to a slurry of PFAparticles in a solvent, any order of combination of the catalyticcomponent, the activator component, PFA, and solvent may be used in thepractice of the present invention. Non-limiting examples of methods ofcombination involving varying order of addition include: adding asolution of the activator component in solvent to a slurry of the PFA insolvent, followed by addition a solution of the catalytic component insolvent; adding a solution of the catalytic component in solvent to aslurry of the PFA in solvent, followed by addition of a solution of theactivator component in solvent; adding a slurry of PFA in solvent to asolution of catalytic component, activator component, and solvent;adding a solution of catalytic component, activator component, andsolvent to dry PFA; adding a solution of catalytic component in solventto dry PFA, followed by addition of a solution of activator component insolvent; or adding a solution of activator component in solvent to dryPFA, followed by addition of a solution of catalytic component insolvent. Further methods involving use of either or both catalyticcomponent and activator component can also be practiced in the presentinvention. Furthermore, multiple solvents may be used. When more thanone solvent is used, it is preferred that those solvents are misciblewith one another. It is further understood that, in any of the methodsof combination enumerated: one or more activator components may be used;one or more catalytic components may be used; and one or more PFAs maybe used.

Ziegler-Natta based PFA catalysts of the present invention for PE, PP,and their copolymers can be made by a variety of methods which will beclear to one skilled the art. The TiCl₄/MgCl₂ catalyst system is formedwithin the structure of the PFA, imposing the commercially-desirablespheroidal morphology on the resulting catalyst. In this way the PFAcatalyst can be used in any commercial process type (gas phase, bulkmonomer, slurry) to manufacture high bulk density, spherical polymerparticles.

A typical method for producing the Ziegler-Natta based PFA catalyst isto introduce a suitable magnesium precursor into the PFA particle.Preferably a solution of the magnesium species is used. Suitable Mgprecursors include, for example, Grignards, magnesium alkoxides, andmixed Mg/Ti alkoxides. The solvent can be removed to afford a magnesiumimpregnated PFA particle which is then subjected to a suitablechlorinating agent to afford MgCl₂ particles within the PFA. Suitablechlorinating agents are known to those skilled in the art but include,for example, TiCl₄, thionyl chloride, benzoyl chloride. The resultingmagnesium impregnated PFA can then be treated with titaniumtetrachloride to produce the PFA catalyst. (When TiCl₄ is used as thechlorinating agent, treatment with more titanium tetrachloride isoptional.) Typically this last step is carried out at temperatures inthe range of 80–120° C. and then the resulting PFA catalyst is washedwith excess aliphatic hydrocarbon (to remove any soluble titaniumspecies that would cause reactor fouling and, in the case of PP, atacticPP generation). PFA catalysts made in the absence of any electron donorsare suitable for PE production. In addition to any electron donors thatmay be present in tether groups, electron donors can be incorporatedinto the PFA catalyst to enhance catalyst activity and, in the case ofPP, to enhance stereoselectivity. Suitable electron donors include, THF,aromatic esters such as ethylbenzoate, phthalates such as di-n-butylphthalate, and diethers. Preferred electron donor families for PPcatalysts are aromatic esters such as ethylbenzoate, phthalates such asdi-n-butyl phthalate and diethers.

The “catalytic components” usefully employed in accordance with theinvention are organometallic compositions of transition metals. Thetransition metal catalysts preferably are of the Ziegler-Natta type orPhillips type catalysts and more preferably are single site catalysts,such as a Unipol™ catalyst, Insite™ catalyst or Versipol™ catalyst. Themost preferred catalysts are based on organometallic compounds ofzirconium, titanium, chromium, vanadium, iron, cobalt, palladium,copper, and nickel.

Illustrative, but not limiting examples of bis(cyclopentadienyl) group 4metal compounds which may be used as the catalytic component in thepreparation of the catalyst composition of the present invention arelisted below: dihydrocarbyl-substituted bis(cyclopentadienyl)zirconiumcompounds, including bis(cyclopentadienyl)zirconium dichloride,bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconiumdiethyl, bis(cyclopentadienyl)zirconium dipropyl,bis(cyclopentadienyl)zirconium dibutyl, bis(cyclopentadienyl)zirconiumdiphenyl, bis(cyclopentadienyl)zirconium dineopentyl,bis(cyclopentadienyl)zirconium di(m-tolyl),bis(cyclopentadienyl)zirconium di(p-tolyl) and chemically/structurallyrelated compounds; dihydrido-substituted bis(cyclopentadienyl) zirconiumcompounds, including bis(cyclopentadienyl)zirconium dihydride, andchemically/structurally related compounds; hydrido halide-substitutedbis(cyclopentadienyl) zirconium compounds, includingbis(cyclopentadienyl)zirconium hydrido chloride, andchemically/structurally related compounds; hydrocarbylhydride-substituted bis(cyclopentadienyl) zirconium compounds includingbis(cyclopentadienyl)zirconium methyl hydride,bis(pentamethylcyclopentadienyl)zirconium (phenyl)(hydride),bis(pentamethylcyclopentadienyl)zirconium (methyl)(hydride), andchemically/structurally related compounds; (monohydrocarbyl-substitutedcyclopentadienyl)zirconium compounds including(methylcyclopentadienyl)(cyclopentadienyl) zirconium dimethyl,bis(methylcyclopentadienyl)zirconium dimethyl,bis(dibutylcyclopentadienyl)zirconium dimethyl, andchemically/structurally related compounds;(polyhydrocarbyl-substituted-cyclopentadienyl) zirconium compounds,including (dimethylcyclopentadienyl) (cyclopentadienyl) zirconiumdimethyl, bis(dimethylcyclopentadienyl) zirconium dimethyl,bis(pentamethylcyclopentadienyl) zirconium dimethyl, andchemically/structurally related compounds, compounds in which thedimethyl portion is replaced by dichloride;(bridged-cyclopentadienyl)zirconium compounds, including methylenebis(cyclopentadienyl)zirconium dimethyl, methylenebis(cyclopentadienyl)zirconium dihydride, ethylenebis(cyclopentadienyl)zirconium dimethyl,dimethylsilylbis(cyclopentadienyl)zirconium dimethyl,ethylenebis(cyclopentadienyl)zirconium dihydride, dimethylsilylbis(cyclopentadienyl)zirconium dihydride, and chemically/structurallyrelated compounds, and the corresponding dichlorides; chiral andC₂-symmetry compounds; asymetrically bridged-dicylopentadienylcompounds, including methylene(cyclopentadienyl)(1-fluorenyl)zirconiumdimethyl, dimethysilyl(cyclopentadienyl)(1-fluorenyl)zirconiumdihydride, isopropyl(cyclopentadienyl)(1-fluorenyl)zirconium dimethyl,isopropyl(cyclopentadienyl)1-octahydrofluorenyl)zirconium dimethyl,dimethylsil(methylcyclopentadienyl)(1-fluorenyl)zirconium dihydride,methylene(cyclopentadienyl(tetramethylcyclopentadienyl)zirconiumdimethyl, and chemically/structurally related compounds, and thecorresponding dichlorides; racemic and meso isomers of symmetricallybridged substituted dicyclopentadienyl compounds, includingethylenebis(indenyl)zirconium dimethyl,dimethylsilylbis(indenyl)zirconium dimethyl,ethylenebis(tetrahydroindenyl)zirconium dimethyl, anddimethylsilylbis(3-trimethylsilylcyclopentadientyl)zirconium dihydride;zirconacycles, including bis(pentamethylcyclopentadienyl)zirconacyclobutane, bis(pentamethylcyclopentadienyl)zirconacyclopentane, bis(cyclopentadienyl)zirconaindane, and1-bis(cyclopentadienyl)zircona-3-dimethylsila-cyclobutane; olefin,diolefin and aryne ligand substituted bis(cyclopentadienyl)zirconiumcompounds, inncluding bis(cyclopentadienyl) (1,3-butadiene)zirconium,bis(cyclopentadienyl) (2,3-dimethyl-1,3-butadiene)zirconium, andbis(pentamethylcyclopentadienyl)(benzyne)zirconium; andbis(cyclopentadienyl) zirconium compounds in which a substituent on thecyclopentadienyl radical is bound to the metal, including(pentamethylcyclopentadienyl) (tetramethylcyclopentadienylmethylene)zirconium, hydride, (pentamethylcyclopentadienyl),(tetramethylcyclopentadienylmethylne)zirconium phenyl, andchemically/structurally related compounds.

Illustrative, but non-limiting examples of bis(cyclopentadienyl)hafniumand bis(cyclopentadienyl)titanium compounds that, as the catalyticcomponent, usefully comprise the catalyst composition of the presentinvention are disclosed in publications of Alt and Koeppl, such as Chem.Rev., 100, 1205–1222, 2000 and Hlatky, Chem. Rev., 100, 1347–1376, 2000,the contents of which are usefully employed in accordance with theinvention. Chemically and structurally relatedbis(cyclopentadienyl)hafnium compounds and bis(cyclopentadienyl)titaniumcompounds as well as other catalysts of Group 4 metals that are usefulin the catalyst composition of the present invention would be apparentto those skilled in the art based on their respective chemicalstructures and reactivities in olefin polymerizations.

Illustrative, but non-limiting examples of Group 4 and 6 compoundscontaining a cyclopentadienyl ring bridging to a nitrogen group via acarbon or silicon group which may be used in the preparation of thecatalytic composition of the present invention include:

-   dimethylsilycyclopentadienyl-tertbutylamido zirconium dimethyl,-   dimethylsilycyclopentadienyl-tertbutylamido titanium dimethyl,-   dimethylsilytetramethylcyclopentadienyl-tertbutylamido zirconium    dimethyl,-   dimethylsilytertbutylcyclopentadienyl-tertbutylamido zirconium    dimethyl,-   dimethylsilytetramethylcyclopentadienyl-tertbutylamido titanium    dimethyl,-   dimethylsilytertbutylcyclopentadienyl-tertbutylamido titanium    dimethyl,-   dimethylsilytetramethylcyclopentadienyl-tertbutylamido hafnium    dimethyl,-   dimethylsilytertbutylcyclopentadienyl-tertbutylamido hafnium    dimethyl,-   dimethylsilytetramethylcyclopentadienyl-tertbutylamido zirconium    dimethyl,-   ethylenetetramethylcyclopentadienyldimethylamino chromium dimethyl,    and-   the correspondikng dichlorides.

Illustrative but non-limiting examples of Group 4 or 6 metal complexescontaining bidentate, tridentate or other multidentate ligands that, asthe catalytic component, usefully comprise the catalyst composition ofthe present invention include:

-   (NC(CH3)2CH2CH2C(CH3)2N)Cr(CH2C6H5)2, and-   bis[N-(3-t-butylsalicylidene)phenylaminato] zirconium dichloride.

Illustrative but non-limiting examples of Group 8–11 metal complexescontaining bidentate, tridentate or other multidentate ligands that, asthe catalytic component, usefully comprise the catalyst composition ofthe present invention are disclosed in publications of Ittel andBrookhart, such as Chem. Rev., 100, 1169–1203, 2000, Hlatky, Chem. Rev.,100, 1347–1376, 2000, and Gibson, Angew. Chem. Int. Ed. 38, 428–447, thecontents of which are usefully employed in accordance with the presentinvention. Preferred of Group 8–11 catalysts that, as the catalyticcomponent, usefully comprise the catalyst composition of the presentinvention are:

-   {(2,6-iPr₂C₆H₃)—N═C(H)—C(H)═N-(2,6-iPr₂C₆H₃)}NiBr₂,-   {(2,6-iPr₂C₆H₃)—N═C(Me)—C(Me)═N-(2,6-iPr₂C₆H₃)} NiBr₂,-   {(2,6-iPr₂C₆H₃)—N═C(Ph)—C(Ph)═N-(2,6-iPr₂C₆H₃)} NiBr₂,-   {(2,6-Me₂C₆H₃)—N═C(H)—C(H)═N-(2,6-Me₂C₆H₃)}NiBr₂,-   {(2,6-Me₂C₆H₃)—N═C(Me)—C(Me)═N-(2,6-Me₂C₆H₃)}NiBr₂,-   {(2,6-Me₂C₆H₃)—N═C(Ph)—C(Ph)═N-(2,6-Me₂C₆H₃)} NiBr₂,-   {(2,6-iPr₂C₆H₃)—N═C(H)—C(H)═N-(2,6-iPr₂C₆H₃)} Pd(Cl)Me,-   [{(2,6-iPr₂C₆H₃)—N═C(Me)—C(Me)═N-(2,6-iPr₂C₆H₃)} PdMe (NC—Me)]+,-   [{(2,6-iPr₂C₆H₃)—N═C(Ph)—C(Ph)═N-(2,6-iPr₂C₆H₃)) PdMe (NC—Me)]+,-   [{(2,6-iPr₂C₆H₃)—N═C(H)—C(H)═N-(2,6-iPr₂C₆H₈)} PdMe (NC—Me)]+,-   [{(2,6-iPr₂C₆H₃)—N═C(Me)—C(Me)═N-(2,6-iPr₂C₆H₃)} PdMe (NC—Me)]+,-   [((2,6-iPr₂C₆H₃)—N═C(Ph)—C(Ph)═N-(2,6-iPr₂C₆H₃)}PdMe (NC—Me)]+,-   [{(2,6-iPr₂C₆H₃)—N═C(Me)—C(Me)═N-(2,6-iPr₂C₆H₃)} NiMe (OEt₂)]+,-   [{(2,6-iPr₂C₆H₃)—N═C(Ph)—C(Ph)═N-(2,6-iPr₂C₆H₃)} NiMe (OEt₂)]+,-   {[(2,6-PhN═C(CH₃))₂C₅H₃N]CoCl₂, ([(2,6-PhN═C(CH₃))₂C₅H₃N] FeCl₂},-   {[(2,6-PhN═C(CH₃)₂C₅H₃N] CoCl₃}, {[(2,6-PhN═C(CH₃))₂C₅H₃] FeCl₃},    and-   bis (2,2′-bipyridyl) iron diethyl.

Chemically and structurally related catalytically active Iron, Cobalt,Nickel, Palladium, and Copper compounds as well as other catalysts ofGroup 8–11 metals that are useful in the catalyst composition of thepresent invention would be apparent to those skilled in the art based ontheir respective chemical structures and reactivities in olefinpolymerizations.

The “catalytic component” of the present invention is typically acomponent in the “PFA catalyst” of the present invention at aconcentration of 0.0001 mmole/gram to 2.00 mmoles/g, preferably 0.0001mmole/g to 1.5 mmoles/g, more preferably 0.0005 mmole/g to 1.5 mmoles/g,and most preferably 0.001 mmole/g to 1.00 mmole/g, defined as mmoles ofmetal per gram of PFA (dry weight).

Activator components for these PFA catalysts may be trialkylaluminumssuch as triethyl or triisobutyl aluminum. When used for PP manufacture,the catalysts are typically used in combination with third components(electron donors) to enhance stereoselectivity. In the case of catalystswith aromatic esters as internal donors the preferred third components(or external donors) are also aromatic esters such aspara-ethoxy-ethylbenzoate and the like, where phthalates are used asinternal donors the preferred external donors are silanes such asdialkyl dialkoxy silanes like dicyclohexyldipropoxy silanes, in the caseof the diethers no external donor is strictly essential but optionallythe silane donors can be used to further improve stereoselectivity.

Illustrative, but non-limiting examples of the “activator component”that usefully comprises the “PFA catalyst” of the present invention aredisclosed in publications of Chen and Marks, such as Chem. Rev., 100,1391–1434, 2000, Coates, such as Chem. Rev., 100, 1223–1252, 2000,Resconi et al, such as Chem. Rev., 100, 1253–1346, 2000, Fink et al,such as Chem. Rev., 100, 1377–1390, 2000 Alt and Koeppl, such as Chem.Rev., 100, 1205–1222, 2000 and Hlatky, Chem. Rev., 100, 1347–1376, 2000,the contents of which are usefully employed in accordance with theinvention. Activator components usefully comprising the catalystcomposition of the present invention, for example, include: aluminumalkyls such as Al(C2H5)3, Al(CH2CH(CH3)2)3, Al(C3H7)3, Al((CH2)3CH3)3,Al((CH2)5CH3)3, Al(C6F5)3, Al(C₂H5)2Cl, A12(C2H5)3C12), A1C13;aluminoxanes such as methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, butylaluminoxane,heptylaluminoxane and methylbutylaluminoxane; and combinations thereof.Both stoichiometric and non-stoichiometric quantities of activatorcomponents are usefully employed in the “PFA catalyst” of the presentinvention. Chemically and structurally useful aluminum compounds as wellas other catalysts of Group 13 elements that are useful in the catalystcomposition of the present invention would be apparent to those skilledin the art based on their respective chemical structures and activitiesin olefin polymerizations.

The activator component further comprises hydroxyaluminoxanes.Hydroxyaluminoxanes, and methods of preparing them, are disclosed inU.S. Pat. No. 6,160,145. The hydroxyaluminoxane has a hydroxyl groupbonded to at least one of its aluminum atoms. To form thesehydroxyaluminoxanes, a sufficient amount of water is reacted with analkyl aluminum compound to result in formation of a compound having atleast one HO—Al group and having sufficient stability to allow reactionwith a d- or f-block organometallic compound to form a hydrocarbon.

The alkyl aluminum compound used in forming the hydroxyaluminoxanereactant can be any suitable alkyl aluminum compound other thantrimethylaluminum. Thus at least one alkyl group has two or more carbonatoms. Preferably each alkyl group in the alkyl aluminum compound has atleast two carbon atoms. More preferably each alkyl group has in therange of 2 to about 24, and still more preferably in the range of 2 toabout 16 carbon atoms. Most preferred are alkyl groups that have in therange of 2 to about 9 carbon atoms each. The alkyl groups can be cyclic(e.g., cycloalkyl, alkyl-substituted cycloalkyl, orcycloalkyl-substituted alkyl groups) or acyclic, linear or branchedchain alkyl groups. Preferably the alkyl aluminum compound contains atleast one, desirably at least two, and most preferably three branchedchained alkyl groups in the molecule. Most preferably each alkyl groupof the aluminum alkyl is a primary alkyl group, i.e., the alpha-carbonatom of each alkyl group carries two hydrogen atoms.

Suitable aluminum alkyl compounds which may be used to form thehydroxyaluminoxane reactant include dialkylaluminum hydrides andaluminum trialkyls. Examples of the dialkylaluminum hydrides includediethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminumhydride, di(2,4,4-trimethylpentyl)aluminum hydride,di(2-ethylhexyl)aluminum hydride, di(2-butyloctyl)aluminum hydride,di(2,4,4,6,6-pentamethylheptyl)aluminum hydride,di(2-hexyldecyl)aluminum hydride, dicyclopropylcarbinylaluminum hydride,dicyclohexylaluminum hydride, dicyclopentylcarbinylaluminum hydride, andanalogous dialkylaluminum hydrides. Examples of trialkylaluminumcompounds which may be used to form the hydroxyaluminoxane includetriethylaluminum, tripropylaluminum, tributylaluminum,tripentylaluminum, trihexylaluminum, triheptylaluminum,trioctylaluminum, and their higher straight chain homologs;triisobutylaluminum, tris(2,4,4-trimethylpentyl)aluminum,tri-2-ethylhexylaluminum, tris(2,4,4,6,6-pentamethylheptyl)aluminum,tris(2-butyloctyl)aluminum, tris(2-hexyldecyl)aluminum,tris(2-heptylundecyl)aluminum, and their higher branched chain homologs;tri(cyclohexylcarbinyl)aluminum, tri(2-cyclohexylethyl)aluminum andanalogous cycloaliphatic aluminum trialkyls; andTri(pentafluoro)aluminum. Triisobutylaluminum has proven to be anespecially desirable alkyl aluminum compound for producing ahydroxyaluminoxane. Hydroxyisobutylaluminoxane (HOIBAO) is a preferredhydroxyaluminoxane. The hydroxyisobutylaluminoxane is essentially devoidof unreacted triisobutylaluminum. Useful activator components furtherinclude aluminoxane salt compositions (aluminoxinates) as disclosed inU.S. Pat. No. 5,922,631.

Activator components useful in the present invention further includeorganic borane compounds, inorganic borane compounds, and borate anions.Preferred examples of boron containing activator components employed inthe PFA catalyst of the present invention are trifluoroborane,triphenylborane, Tris(4-fluorophenyl)borane,Tris(3,5-difluorophenyl)borane, Tris(4-fluoromethylphenyl)borane,Tris(pentafluorophenyl)borane, Tris(tolyl)borane,Tris(3,5-dimethylphenyl)borane, Tris(3,5-difluorophenyl)borane,Tris(3,4,5-trifluorophenyl)borane, Dimethylanilinium (pentafluorophenyl)borate, sodium [B{3,5-(CF₃)₂C₆F₃}₄], [H(OEt₂)₁[B{3,5-(CF₃)₂C₆F₃}₄]. Bothstoichiometric and non-stoichiometric quantities of activators areusefully employed in the catalyst matrix of the present invention usingtriaryl carbenium tetraarylborates, N,N-dialkylanilinium salts such asN,N-dimethylanilinium tetra(pentafluorophenyl)borate,N,N-diethylanilinium tetra(phenyl)borate, N,N-2,4,6-pentamethylaniliniumtetraphenylborate and chemically related Group 13 compounds; dialkylammonium salts such as di(i-propyl)ammoniumtetra(pentafluorophenyl)borate, dicyclohexylammonium tetra(phenyl)boronand chemically related Group 13 compounds; triaryl phosphonium saltssuch as triphenylphosphonium tetraphenylborate,tri(methylphenyl)phosphonium tetra(phenyl)borate,tri(dimethylphenyl)phosphonium tetra(phenyl)borate and chemicallyrelated Group 13 compounds. Any complex anions or compounds forming suchanions that exhibit an ability to abstract and activate the metalcompounds would be within the scope of the catalyst composition of thepresent invention. Chemically and structurally useful boron compoundsthat are useful in the PFA catalyst of the present invention would beapparent to those skilled in the art based on their respective chemicalstructures and activities in olefin polymerizations.

The “activator component” of the present invention is an aluminumcontaining activator, it is typically present at a concentration of 0.01mmole/gram to 50 mmoles/g, preferably 0.01 mmole/g to 20 mmoles/g, morepreferably 0.05 mmole/g to 10 mmoles/g, and most preferably 0.1 mmole/gto 5 mmole/g, defined as mmoles of aluminum per gram of PFA (dryweight). When the activator component is boron based, it is typicallypresent at a concentration of 0.0001 mmole/gram to 50 mmoles/g,preferably 0.0001 mmole/g to 20 mmoles/g, more preferably 0.0005 mmole/gto 10 mmoles/g, and most preferably 0.001 mmole/g to 5 mmole/g, definedas mmoles of boron per gram of PFA (dry weight).

The present invention also provides a general process for the productionof specific polyolefins by judicious selection of catalytic component,activator component, and PFA. The process comprises polymerizing olefinssuch as ethylene or propylene alone or in the presence of higherα-olefins, diolefins or cycloolefins in the presence of the PFAcatalyst. Combinations of the above catalytic components within the PFAcatalyst have utility in accordance with process of the presentinvention.

The advantages of the invention are obtained in the ability of thetether groups of the PFA to react with, or otherwise interact with,commercially important catalytic components, and optionally activatorcomponents, for olefin polymerization, the resulting PFA catalystshaving utility in the polymerization of a range of olefin monomers. Thereaction of the tether groups of the PFA with the catalytic componentsand activator components affords additional advantages, namely,stabilizing, activating and supporting the catalysts. In addition,precision control of the structure and composition of the PFA ispossible such that fragmentation is confined to the olefinpolymerization process, and then only to the extent that thefragmentation domains move away from one another without detaching fromthe PFA particle.

The present invention is directed to a PFA catalyst for thepolymerization of olefins, the PFA catalyst being formed by reaction, orother interaction, of a PFA, a catalytic component, and, optionally, anactivator component. The PFA catalyst has utility in a general catalyticprocess for polymerization of olefins. In particular, the process ofcatalytically converting ethylene to higher molecular weightpolyethylene homopolymers, such as high density polyethylene (HDPE) andlinear low density polyethylene (LLDPE), and copolymers withalpha-olefins such as 1-butene, 1-hexene and 1-octene. These olefinpolymers are intended for processing into articles of manufacture byextrusion, injection molding, thermoforming, rotational molding, hotmelt processing and related techniques. In addition, the polyolefins ofthe present invention are homopolymers of ethylene and propylene,copolymers of ethylene and propylene with higher alpha-olefins ordiolefins, and stereoregular polymers of propylene.

In accordance with the present invention, polyolefins can be preparedfrom olefin monomers using a PFA catalyst in a catalytic process witholefin monomers such as unbranched aliphatic olefins having from 2 to 12carbon atoms, branched aliphatic olefins having from 4 to 12 carbonatoms, unbranched and branched aliphatic α-olefins having from 2 to 12carbon atoms, conjugated olefins having 4 to 12 carbon atoms, aromaticolefins having from 8 to 20 carbons, unbranched and branchedcycloolefins having 3 to 12 carbon atoms, unbranched and branchedacetylenes having 2 to 12 carbon atoms, and combinations thereof. Alsoin accordance with the invention, olefin monomer further comprises polarolefin monomers having from 2 to 60 carbon atoms and at least one atomsuch as O, N, B, Al, S, P, Si, F, Cl, Br and combinations thereof.

In particular, the olefin monomer is ethylene, propene, 1-butene,1-hexene, butadiene, 1,6-hexadiene, styrene, alpha-methylstyrene,cyclopentene, cyclohexene, cyclohexadiene, norbornene, norbornadiene,cyclooctadiene, divinylbenzene, trivinylbenzene, acetylene, diacetylene,alkynylbenzene, dialkynylbenzene, ethylene/1-butene,ethylene/isopropene, ethylene/1-hexene, ethylene/1-octene,ethylene/propene, ethylene/cyclopentene, ethylene/cyclohexene,ethylene/butadiene, ethylene/1,6-hexadiene, ethylene/styrene,ethylene/acetylene, propene/1-butene, propene/styrene,propene/butadiene, propylene/1-hexene, propene/acetylene,ethylene/propene/1-butene, ethylene/propene/1-hexene,ethylene/propene/1-octene, and various combinations thereof.

In one embodiment, the PFA catalyst of the present invention can beusefully employed with many catalytic components and, optionally,activator components exhibiting high activities in ethylenehomopolymerization and copolymerization of ethylene/higher α-olefins,allowing the synthesis of ethylene homopolymers and copolymers withnarrow molecular weight distributions and/or homogeneous branchingdistributions. The HDPE and LLDPE resins prepared are intended for usein: the production of films with relatively high impact strength andclarity; fabrication into articles and useful objects by extrusion,injection molding, thermoforming, rotational molding, holt meltprocessing; processing of polyethylenes having monodisperse, inorganicparticulate additives or modifiers; and the processing of coatedsurfaces, articles and useful objects using polymers comprisingethylene.

An embodiment illustrative of the general utility of the PFA catalyst isthe production of polyethylene. All three classes of the polyethylene(PE), namely high density polyethylene (HDPE), low density polyethylene(LDPE) and linear low density polyethylene (LLDPE), each class of whichrequires a different catalyst system currently, can be prepared usingthe PFA catalyst of the present invention. HDPE is a linear,semi-crystalline ethylene homopolymer prepared using Ziegler-Natta andChromium based polymerization methods. LLDPE is a random copolymer ofethylene and α-olefins (such as 1-butene, 1-hexene or 1-octene) preparedcommercially using Ziegler-Natta, Chromium based or metallocene basedcatalysts. LDPE is a branched ethylene homopolymer prepared commerciallyusing a high temperature and high pressure process. HDPE, LDPE and LLDPEcan all be prepared by reacting olefins with the PFA catalysts of thepresent invention.

Another embodiment illustrative of the general utility of the PFAcatalyst is the production of copolymers of ethylene and higheralpha-olefins. When making polymers, Ziegler-Natta catalysts typicallyproduce polyethylene resins of moderately broad to very broad molecularweight distribution, as characterized by MWD values greater than 6. Theoccurrence of broad molecular weight distributions in such catalystsystems is attributed to inhomogeneous catalytic sites. By reacting aPFA with a Ziegler-Natta catalyst and forming the PFA catalyst of thepresent invention, the polymerization of ethylene can lead to narrowermolecular weight distributions, as characterized by MWD values less than6.

In another useful embodiment of the present invention, polycycliccopolymers are prepared which comprise repeating units copolymerizedfrom at least one polycycloolefin monomer and at least one acrylate ormethacrylate monomer. Used herein, the term polycycloolefin means anorbornene-type monomer. The term norbornene-type monomer is meant toinclude norbornene, substituted norbornene(s), and any higher cyclicderivatives thereof so long as the monomer contains at least onenorbornene or substituted norbornene moiety. The substituted norbornenesand higher cyclic derivatives thereof contain a pendant hydrocarbylsubstituent(s) or a functional substituent(s) containing an oxygen atom.These polycyclic copolymers and a list of the monomers useful inpreparing them are disclosed in US-B1-2001-6,265,506 andUS-B1-2001-6,303,724.

In the process of the present invention, olefins such as ethylene orpropylene, either alone or together with higher alpha-olefins having 3or more carbons atoms, are polymerized in the presence of a PFAcatalyst, itself formed by combining a PFA with at least one catalyticcomponent and at least one activator component. In accordance with thepresent invention, one can also produce olefin copolymers of ethyleneand higher alpha-olefins having 3–20 carbon atoms. Comonomer content canbe controlled through selection of PFA, catalytic component, andactivator component.

Precision fragmentation assemblages of the present invention are alsouseful as delivery structures, affording controlled release of activeingredients including, but not limited to, pharmaceuticals, biocides,herbicides, mildewcides, insecticides, fungicides, fertilizers,cosmetics, fragrances, liquid crystals, and colorants such as pigments,pleochroic dyes, and non-pleochroic dyes. They are especially useful forproviding dual and multiple release mechanisms, including triggeredrelease.

The PFAs of the present invention may further be used as enzymeimmobilization supports, particularly when controlled degradation of thesupport is desired.

The PFAs of the present invention are also useful as macroreticularresins. The PFAs are suitable for essentially any application for whichtraditional macroreticular resins currently used. In particular, PFAsoffer advantages of traditional macroreticular resins in affordingbetter control of access of substances to the interior of the PFArelative to traditional macroreticular resin, and better flowcharacteristics (e.g., lower pressure drops) in packed columns. The PFAsmay be suitably functionalized (e.g., with tether groups having acidicor basic functionality) to produce ion exchange resins. Beyond sphericalparticles, PFAs may be produced as monoliths in which the PFA is amonolithic structure made in essentially any shape and any size. Forexample, the PFA monolith have a cylindrical shape, having a diameter ofseveral centimeters and a length of a several meters.

EXPERIMENTAL

Determination of level of ethylenically unsaturated groups in PFAs.Solid state ¹³C NMR (nuclear magnetic resonance) was used tocharacterize and quantify the amount of ethylenically unsaturated groupscontained in the PFAs useful in the present invention.

Determination of porosity. The porosities of PFAs described herein byexample were measured by Nitrogen adsorption according to methodsdisclosed by Brunauer, et al., J. Am. Chem Soc. 60, 309 (1938).

Molecular Weight Determination using Gel Permeation Chromatography(GPC). Gel Permeation Chromatography, otherwise known as size exclusionchromatography, actually separates the members of a distribution ofpolymer chains according to their hydrodynamic size in solution ratherthan their molar mass. The system is then calibrated with standards ofknown molecular weight and composition to correlate elution time withmolecular weight. The techniques of GPC are discussed in detail inModern Size Exclusion Chromatography, W. W. Yau, J. J Kirkland, D. D.Bly; Wiley-Interscience, 1979, and in A Guide to MaterialsCharacterization and Chemical Analysis, J. P. Sibilia; VCH, 1988, p.81–84.

For example, the molecular weight information for a low molecular weightsample (e.g., 10,000) may be determined as follows: The sample (anaqueous emulsion containing low molecular weight particles) is dissolvedin THF at a concentration of approximately 0.1% weight sample per volumeTHF, and shaken for 6 hours, followed by filtration through a 0.45 μmPTFE (polytetrafluoroethylene) membrane filter. The analysis isperformed by injecting 100 μl of the above solution onto 3 columns,connected in sequence and held at 40° C. The three columns are: one eachof PL Gel 5 100, PL Gel 5 1,000, and PL Gel 5 10,000, all available fromPolymer Labs, Amherst, Mass. The mobile phase used is THF flowing at 1ml/min. Detection is via differential refractive index. The system wascalibrated with narrow polystyrene standards. PMMA-equivalent molecularweights for the sample are calculated via Mark-Houwink correction usingK=14.1×10⁻³ ml/g and a=0.70 for the polystyrene standards andK=10.4×10⁻³ ml/g and a=0.697 for the sample.

EXPERIMENTAL EXAMPLES

Some embodiments of the invention will now be described in detail in thefollowing Examples. The following abbreviations shown in Table 1 areused in the examples.

TABLE 1 Abbreviations Abbreviation Description ALMA Allyl methacrylateBA Butyl acrylate BMA Butyl methacrylate EA Ethyl acrylate GC Gaschromatograph GMA Glycidyl methacrylate HEMA Hydroxyethyl methacrylateHPLC High performance liquid chromatography Init. Initiator IR Infraredspectroscopy MAA Methacrylic acid MMA Methyl methacrylate MCPBAm-chloroperoxybenzoic acid (nominal 75% active) AOH allyl alcohol StyStyrene

Example 1.1

Preparation of Fragmentation Domains by Emulsion Polymerization.

Initially, 1831 grams of water, 7 grams of sodium lauryl sulfate (28%solution in water), and 0.5 grams of acetic acid were added to a 5 literround bottom flask fitted with a paddle stirrer, thermometer, nitrogensparge, and heating mantel. A first monomer emulsion was preparedseparately by emulsifying 800 grams of styrene, 200 grams of divinylbenzene, 36 grams of sodium lauryl sulfate (28% solution in water), and311 grams of water in a 2 liter beaker, using a high speed mixer. Aninitiator solution was prepared by mixing, in a 150 ml beaker, 2 gramsof t-butyl hydroperoxide (70% solution in water) with 98 grams of water.A reducing agent solution was prepared by mixing, in a 150 ml beaker, asolution of 2 grams of sodium hydroxy methane sulfinate (78% as ahydrate) with 98 grams of water. The kettle charge was heated to 70° C.The monomer emulsion, initiator solution, and reducing agent mixtureswere fed to the kettle simultaneously, but separately, while maintaininga reaction temperature of 70° C. All feeds were begun at the same time.The duration of the monomer feed was 75 minutes, while the duration ofthe other feeds was 100 minutes. The batch was held for 30 minutes aftercompletion of the feeds, and then cooled to 25° C. The final polymercontent of the fragmentation domain latex (here, the “first polymer” isa styrene/DVB copolymer) was determined gravimetrically to be 29%(non-volatile weight/total latex weight), representing a 97% yield ofpolymer (the theoretical value for final polymer content was 30%).Residual styrene monomer, determined by headspace gas chromatography,was less than 500 parts per million in the fragmentation domain latexsample. The fragmentation domain particle size was measured to be 150 nmby light scattering and scanning electron microscopy. Some of the latexwas dried and then extracted with toluene. The toluene soluble polymerfraction was less than 0.2% by weight of the dried fragmentation domainsample, indicating a very high degree of crosslinking in thefragmentation domains.

Example 1.2

Preparation of Fragmentation Domains by Emulsion Polymerization.

Initially, 1831 grams of water, 7 grams of sodium lauryl sulfate (28%solution in water), and 0.5 grams of acetic acid are added to a 5 literround bottom flask fitted with a paddle stirrer, thermometer, nitrogensparge, and heating mantel. A first monomer emulsion is preparedseparately by emulsifying 1,000 grams of a first monomer composition(see monomers 1, 2, and 3 in Table 1.2), 36 grams of sodium laurylsulfate (28% solution in water), and 311 grams of water in a 2 literbeaker, using a high speed mixer. An initiator solution is prepared bymixing, in a 150 ml beaker, 2 grams of t-butyl hydroperoxide (70%solution in water) with 98 grams of water. A reducing agent solution isprepared by mixing, in a 150 ml beaker, a solution of 2 grams of sodiumhydroxy methane sulfinate (78% as a hydrate) with 98 grams of water. Thekettle charge is heated to 70° C. The monomer emulsion, initiatorsolution, and reducing agent mixtures are fed to the kettlesimultaneously, but separately, while maintaining a reaction temperatureof 70° C. All feeds are begun at the same time. The duration of themonomer emulsion feed is 75 minutes, while the duration of the otherfeeds is 100 minutes. The batch is held for 30 minutes after completionof the feeds, and then cooled to 25° C. The final polymer content of thefragmentation domain latex (here, the “first polymer” has thecomposition, as polymerized units, of the monomer composition), asdetermined gravimetrically, is expected to be approximately 29%(non-volatile weight/total latex weight), representing a 97% yield ofpolymer (the theoretical value for final polymer content was 30%).Residual total monomer, determined by headspace gas chromatography,should be less than 500 parts per million in the fragmentation domainlatex sample. The fragmentation domain particle size in nanometers is150 nm by light scattering and scanning electron microscopy. Some of thelatex is dried and then extracted with toluene. The toluene solublepolymer fraction should be less than 0.2% by weight of the driedfragmentation domain sample, indicating a very high degree ofcrosslinking in the fragmentation domains.

TABLE 1.2 Monomer charges for the preparations of Example 1.2. ExampleMonomer 1 Monomer 2 Monomer 3 Number Monomer 1 weight, grams Monomer 2weight, grams Monomer 3 weight, grams 1.2.A MMA 820 ALMA 50 HEMA 130^(a)1.2.B MMA 690 ALMA 50 HEMA 260^(a) 1.2.C MMA 808 ALMA 50 GMA 142^(b)1.2.D MMA 666 ALMA 50 GMA 284^(b) 1.2.E Sty 742 DVB 200 AOH  58^(c)1.2.F Sty 684 DVB 200 AOH 116^(c) 1.2.G DVB 1000 1.2.H MMA 950 ALMA 501.2.I MMA 950 BDMA 50 ^(a)HEMA: 130 g = 1.00 mole; 260 g = 2.00 mole;^(b)GMA: 142 g = 1.00 mole; 284 g = 2.00 mole; ^(c)AOH: 58 g = 1.00mole; 116 g = 2.00 mole).

Example 1.3

Preparation of Fragmentation Domains by Emulsion Polymerization.

Initially, 1793 grams of water, 53.9 grams of Example 1.2 fragmentationdomain latex (particle size=150 nm; used as seed to produce 600 nmfragmentation domains) and 0.5 grams of acetic acid are added to a 5liter round bottom flask fitted with a paddle stirrer, thermometer,nitrogen sparge, and heating mantel. A first monomer emulsion isprepared separately by emulsifying 984.4 grams of a first monomercomposition (see monomers 1, 2, and 3 in Table 1.3), 42.4 grams ofsodium lauryl sulfate (28% solution in water, see Table 1.2), and 311grams of water in a 2 liter beaker, using a high speed mixer. Aninitiator solution is prepared by mixing, in a 150 ml beaker, 2 grams oft-butyl hydroperoxide (70% solution in water) with 98 grams of water. Areducing agent solution is prepared by mixing, in a 150 ml beaker, asolution of 2 grams of sodium hydroxy methane sulfinate (78% as ahydrate) with 98 grams of water. The kettle charge is heated to 70° C.The monomer emulsion, initiator solution, and reducing agent mixturesare fed to the kettle simultaneously, but separately, while maintaininga reaction temperature of 70° C. All feeds are begun at the same time.The duration of the monomer emulsion feed is 75 minutes, while theduration of the other feeds is 100 minutes. The batch is held for 30minutes after completion of the feeds, and then cooled to 25° C. Thefinal polymer content of the fragmentation domain latex (here, the“first polymer” has the composition, as polymerized units, of themonomer composition), as determined gravimetrically, is expected to beapproximately 29% (non-volatile weight/total latex weight), representinga 97% yield of polymer (the theoretical value for final polymer contentwas 30%). Residual total monomer, determined by headspace gaschromatography, should be less than 500 parts per million in thefragmentation domain latex sample. The fragmentation domain particlesize is 600 nanometers as determined by light scattering and scanningelectron microscopy. Some of the latex is dried and then extracted withtoluene. The toluene soluble polymer fraction should be less than 0.2%by weight of the dried fragmentation domain sample, indicating a veryhigh degree of crosslinking in the fragmentation domains.

TABLE 1.3 Monomer charges for the preparations of Example 1.3. Monomer 1Monomer 2 Monomer 3 Example weight, weight, weight, Number Seed^(a)Monomer 1 grams Monomer 2 grams Monomer 3 grams 1.3.A 1.2.A MMA 820 ALMA50 HEMA 130^(b) 1.3.B 1.2.B MMA 690 ALMA 50 HEMA 260^(b) 1.3.C 1.2.C MMA808 ALMA 50 GMA 142^(c) 1.3.D 1.2.D MMA 666 ALMA 50 GMA 284^(c) 1.3.E1.2.F Sty 742 DVB 200 AOH  58^(d) 1.3.F 1.2.G Sty 684 DVB 200 AOH116^(d) 1.3.G 1.2.J DVB 1000 1.3.H 1.2.K MMA 950 ALMA 50 1.3.I 1.2.L MMA950 BDMA 50 ^(a)The seed is a fragmentation domain latex from Example1.2; ^(b)HEMA: 130 g = 1.00 mole; 260 g = 2.00 mole; ^(c)GMA: 142 g =1.00 mole; 284 g = 2.00 mole; ^(d)AOH: 58 g = 1.00 mole; 116 g = 2.00mole).

Examples 2

Preparation of Polymeric Nanoparticles (PNPs)

A 500 mL reactor is fitted with a thermocouple, a temperaturecontroller, a purge gas inlet, a water-cooled reflux condenser withpurge gas outlet, a stirrer, and an addition funnel. To the additionfunnel is charged 201.60 g of a monomer mixture consisting of: monomer1, monomer 2, and, optionally, monomer 3 (see Table 2); 1.60 g of a 75%solution of t-amyl peroxypivalate in mineral spirits (Luperox 554-M-75);and 180.00 g diisobutyl ketone (“DIBK”). The reactor, containing 180.00g DIBK, is then flushed with nitrogen for 30 minutes before applyingheat to bring the contents of the reactor to 75° C. When the contents ofthe reactor reaches 75° C., the monomer mixture in the addition funnelis uniformly charged to the reactor over 90 minutes. Thirty minutesafter the end of the monomer mixture addition, the first of two chaseraliquots, spaced thirty minutes apart and consisting of 0.06 g of a 75%solution of t-amyl peroxypivalate in mineral spirits (Luperox 554-M-75)and 2.00 g DIBK, is added. At the end of the second chaser aliquot, thecontents of the reactor are held 2½ hours at 80° C. to complete thereaction. The resulting polymer is isolated by precipitation withheptane, collected by filtration and dried under vacuum to yield a whitepowder. This material is redissolved in propyleneglycol monomethyletheracetate. The nanoparticles thus formed should have a mean particle sizeof 6 nm and polydispersity of PSD of 1.5, as determined by dynamic laserlight scattering and a molecular weight of 22,500 g/mol with a numberaverage molecular weight of about 14,500 g/mol and Mw/Mn distribution of1.6 as measured by GPC.

TABLE 2 Monomers used to prepare the PNPs of Example 1.4. Monomer 1Monomer 2 Monomer 3 Example weight, weight, weight, Number Monomer 1grams Monomer 2 grams Monomer 3 grams 2.A Sty 16 DVB 4 2.B Sty 13 DVB 4AOH 3 2.C MMA 19 ALMA 1 2.D MMA 16 ALMA 1 HEMA 3

Examples 3.1

Preparation of a Precision Fragmentation Assemblage by CoagulationFollowed by Polymerization.

Initially, 475 grams of water and 25 grams of anhydrous magnesiumsulfate were added to a 3 liter beaker fitted with a paddle stirrer,thermometer, nitrogen sparge, and heating mantel. Asolvent-monomer-initiator solution was prepared by mixing, in a 100 mlbeaker, 19 grams of styrene, 5 grams of divinyl benzene, 48 grams ofxylene, and 0.5 grams of t-butyl peroctoate. Thesolvent-monomer-initiator solution (72.5 grams) was then added to a 150ml beaker, along with 3 grams of sodium lauryl sulfate (28% solution inwater) and 25 grams of water, and emulsified using a high speedultrasonic mixer. The droplet size of the organic phase was less thanabout 1 micron, as determined by optical microscopy. Thesolvent-monomer-initiator emulsion thus formed was then combined with500 grams of the fragmentation domain latex from Example 1.1 to form anemulsion-latex mixture. The magnesium sulfate solution kettle charge wasstirred at 500 RPM at 25° C., while the emulsion-latex mixture was addedduring 5 minutes. In the presence of magnesium sulfate, thefragmentation domain latex and emulsified monomer-solvent-initiatoremulsion co-coagulated into a slurry-like mixture. The resulting slurrymixture was heated to a temperature of 85° C. and held for 120 minutesto cause the monomer to polymerize. The reaction mixture was cooled to25° C., and filtered through a fritted stainless steel funnel with apore size of less than about 1 micron. The filtrate was clear. Theprecision fragmentation assemblage particles were washed with 5,000grams of deionized water. The filter cake was dried in a vacuum oven at60° C. and 0.1 atmospheres for two days. The weight of PFA product was162 grams (96% of the theoretical total). The powdery PFA sample wasexamined by scanning electron microscopy and found to have a particlesize of about 1–20 microns (polydispersity of PSD ˜2). The individualparticles were porous.

Example 3.1 demonstrates that agglomeration (here, coagulation) offragmentation domains, monomer, and porogen (toluene) may be followed,to good effect, by polymerization of the monomer to form second polymerwithin the interstitial space among the fragmentation domains. Duringthe polymerization process, polymerization induced phase separation(PIPS) occurs in which the second polymer precipitates from the porogen(xylene) to form a connecting phase in the fragmentation zone (withinthe interstitial space) and a pore phase. In this example, the porephase is first occupied by xylene which is then replaced by air duringdrying.

Example 3.2

Preparation of a Precision Fragmentation Assemblage by SpheroidCoagulation Followed by Polymerization.

Intially, 497.5 grams of water and 2.5 grams of anhydrous magnesiumsulfate are added to a 3 liter beaker fitted with a paddle stirrer,thermometer, nitrogen sparge, and heating mantel. Asolvent-monomer-initiator solution is prepared by mixing, in a 100 mlbeaker, 19 grams of styrene, 5 grams of divinyl benzene, 48 grams ofxylene, and 0.5 grams of t-butyl peroctoate. Thesolvent-monomer-initiator solution (72.5 grams) is then added to a 150ml beaker, along with 3 grams of sodium lauryl sulfate (28% solution inwater) and 25 grams of water, and emulsified using a high speedultrasonic mixer. The droplet size of the organic phase is less thanabout 1 micron, as determined by optical microscopy. Thesolvent-monomer-initiator emulsion thus formed is then combined with 500grams of the fragmentation domain latex to form an emulsion-latexmixture (fragmentation domain latexes 1.2.A through 1.2.I are usedherein to prepare PFAs 3.2.A through 3.2.I, respectively). The magnesiumsulfate solution kettle charge is stirred at 500 RPM at 65° C. while theemulsion-latex mixture is added during 1 minute. In the presence ofmagnesium sulfate, the fragmentation domain latex and emulsifiedmonomer-solvent-initiator emulsion co-coagulate into a slurry-likemixture in which the bulk particles formed are spheroidal in shape anddisplay a narrow particle size distribution. The resulting slurrymixture is heated to a temperature of 85° C. and held for 120 minutes tocause the monomer to polymerize. The reaction mixture is cooled to 25°C., and filtered through a fritted stainless steel funnel with a poresize of less than about 1 micron. The filtrate should be clear. Theprecision fragmentation assemblage particles (PFA particles) are washedwith 5,000 grams of deionized water. The filter cake is dried in avacuum oven at 60° C. and 0.1 atmospheres for two days. The weight ofPFA product is 162 grams (96% of the theoretical total). The PFAparticles have an average particle size of 50 microns and apolydispersity of the particle size distribution of 1.3. PFAcharacteristics, including ethylene polymerization efficiency of PFAcatalysts prepared from them by experimental methods given infra, aregiven in Table 3.2.

TABLE 3.2 Characteristics of variously functionalized PFA particleshaving fragmentation domains with average particle size of 150nanometers. mmoles residual mmoles mmoles Pore surface grams double OHepoxy volume area of polyolefin/ polyolefin PFA bonds/g groups/ggroups/g of PFA, PFA, metal gram ave. P.S., Number PFA PFA PFA cc/g m²/gcomplex activator PFA mm 3.2.A 0.17 0.86 0.00 0.33 45 BBCZC^(a) MAO 21,780^(d) 1.40 3.2.B 0.19 1.09 0.00 0.33 45 BBCZC MAO 24,572 1.453.2.C 0.17 0.00 0.86 0.33 45 BBCZC MAO 15,593 1.25 3.2.D 0.17 0.00 1.720.33 45 BBCZC MAO 21,632 1.39 3.2.E 0.46 0.86 0.00 0.33 45 BBCZC MAO17,443 1.30 3.2.F 0.46 1.72 0.00 0.33 45 BBCZC MAO 24,198 1.45 3.2.G2.05 0.00 0.00 0.33 45 ^(b) ^(b) 23,010 1.42 3.2.H 0.17 0.00 0.00 0.3345 ^(c) ^(c) 11,239 1.12 3.2.I 0.07 0.00 0.00 0.33 45 ^(b) ^(b) 10,8101.11 ^(a)BBCZC is the metal complex (BuCp)₂ZrCl₂; ^(b)PFA catalyst isprepared using the method of example H.1 wherein the catalytic componentis biscyclopentadienyl zirconium dimethyl and the activator component isN,N-dimethylanilinium tetra(pentafluorophenyl)borate; ^(c)PFA catalystis prepared using the method of example H.2 wherein the catalyticcomponent and activator component are prepared from the reaction ofmagnesium ethoxylate with an excess of titanium tetrachloride;^(d)efficiencies and polyolefin particle sizes are in all casesevaluated using the method of example J.

Example 3.3

Preparation of a Precision Fragmentation Assemblage by SpheroidCoagulation Followed by Polymerization.

The procedure of Example 3.2 is followed in this example to prepare thePFAs for which characteristics are listed in Table 3.3. PFA samples3.3.A through 3.3.I are prepared by the 65° C. coagulation offragmentation domain latexes 1.3.A through 1.3.I, respectively, alongwith solvent, monomer, and initiator. The PFA particles have an averageparticle size of 50 microns and a polydispersity of the particle sizedistribution of 1.3. PFA characteristics, including ethylenepolymerization efficiency of PFA catalysts prepared from them byexperimental methods given infra, are given in Table 3.3.

TABLE 3.3 Characteristics of variously functionalized PFA particleshaving fragmenation domains with average particle size of 600nanometers. mmoles poly- residual mmoles mmoles Pore surface gramsolefin double OH epoxy volume area of polyolefin/ average PFA bonds/ggroups/g groups/g of PFA, PFA, metal gram P.S., Number PFA PFA PFA cc/gm²/g complex activator PFA mm 3.3.A 0.17 0.86 0.00 0.33 22 BBCZC^(a) MAO  9,585^(d) 1.06 3.3.B 0.19 1.09 0.00 0.33 22 BBCZC MAO 10,556 1.103.3.C 0.17 0.00 0.86 0.33 22 BBCZC MAO  9,585 1.06 3.3.D 0.17 0.00 1.720.33 22 BBCZC MAO 13,298 1.18 3.3.E 0.46 0.86 0.00 0.33 22 BBCZC MAO10,722 1.10 3.3.F 0.46 1.72 0.00 0.33 22 BBCZC MAO 14,875 1.23 3.3.G2.05 0.00 0.00 0.33 22 ^(b) ^(b) 14,145 1.21 3.3.H 0.17 0.00 0.00 0.3322 ^(c) ^(c)  6,909 0.95 3.3.I 0.07 0.00 0.00 0.33 22 ^(b) ^(b)  6,6450.94 ^(a)BBCZC is the metal complex (BuCp)2ZrCl2; ^(b)PFA catalyst isprepared using the method of example H.1 wherein the catalytic componentis biscyclopentadienyl zirconium dimethyl and the activator component isN,N-dimethylanilinium tetra(pentafluorophenyl)borate; ^(c)PFA catalystis prepared using the method of example H.2 wherein the catalyticcomponent and activator component are prepared from the reaction ofmagnesium ethoxylate with an excess of titanium tetrachloride;^(d)efficiencies and polyolefin particle sizes are in all casesevaluated using the method of example J.

Example 3.4

Preparation of PFAs. Variations in: Amount of Fragmentation Zone,Fragmentation Domain Latex, Second Polymer, Crosslinking Monomer inSecond Polymer, and PNP; and Tg of Second Polymer.

The Precision Fragmentation Assemblages of this example are preparedaccording to the procedure of Example 3.2, except that thesolvent-monomer-initiator solution was prepared as follows: Asolvent-monomer-initiator solution is prepared by mixing, in a 100 mlbeaker, monomer 1, monomer 2, monomer 3 (Table 3.4.d only), PNPsolution, xylene, and 0.5 grams of t-butyl peroctoate (see Tables 3.4.a,b, and d for quantities). The fragmentation domain latex is that ofExample 1.1 for Examples 3.4.A and 3.4.B. The fragmentation domain latexis as indicated in Table 3.4.d for Examples 3.4.D. The fragmentationdomain latex is added to the magnesium sulfate solution maintained at65° C. in all cases. The PFA particles have an average particle size of50 microns and a polydispersity of the particle size distribution of1.3. PFA characteristics, including ethylene polymerization efficiencyof PFA catalysts prepared from them by experimental methods given infra,are given in Table 3.4.a.1.

TABLE 3.4.a Monomer, solvent and PNP solution charges for Example 3.4.A.Frag. domain Mon. 1, Mon. 2, PNP^(a) PNP Xylene in Total latex StyreneDVB Xylene solution solution PNP weight of Example weight, weight,weight, weight, weight, wt % solution, xylene, Number grams grams gramsgrams grams PNP grams grams 3.4.A.1 498.9 19.08 5.02 48.22 48.22 3.4.A.2498.9 5.73 1.51 65.09 65.09 3.4.A.3 498.9 1.15 0.30 70.88 70.88 3.4.A.4374.1 28.63 7.53 72.34 72.34 3.4.A.5 374.1 8.59 2.26 97.65 97.65 3.4.A.6374.1 1.72 0.45 106.33 106.33 3.4.A.7 498.88 22.90 1.21 48.22 48.223.4.A.8 498.88 23.62 0.48 48.22 48.22 3.4.A.9 498.88 23.99 0.12 48.2248.22 3.4.A.10 498.88 19.04 5.06 12.06 36.16 20 28.93 40.99 3.4.A.11498.88 19.04 5.06 12.06 36.17 40 21.70 33.76 3.4.A.12 498.88 11.43 3.0421.70 36.16 20 28.93 50.63 3.4.A.13 498.88 11.43 3.04 21.70 36.17 4021.70 43.4 ^(a)PNP is 2.A with composition Sty/DVB = 80/20 (weightbasis).

TABLE 3.4.a.1 Characteristics PFA particles varying in fragmentationzone size, amount, and crosslinking of second polymer, and PNP contentwherein the second polymer has a Tg greater than room temperature.mmoles grams poly- residual mmoles mmoles Pore surface poly- olefindouble OH epoxy volume area of olefin/ average PFA bonds/g groups/ggroups/g of PFA, PFA, metal gram P.S., Number PFA PFA PFA cc/g m²/gcomplex activator PFA mm 3.4.A.1 0.46 0.00 0.00 0.34 46 ^(a) ^(a) 12,607^(c) 1.16 3.4.A.2 0.46 0.00 0.00 0.50 40 ^(b) ^(b) 11,290 1.123.4.A.3 0.46 0.00 0.00 0.56 37 ^(a) ^(a) 10,603 1.10 3.4.A.4 0.47 0.000.00 0.58 60 ^(a) ^(a) 16,969 1.28 3.4.A.5 0.46 0.00 0.00 0.95 54 ^(b)^(b) 15,095 1.24 3.4.A.6 0.46 0.00 0.00 1.12 43 ^(a) ^(a) 11,876 1.143.4.A.7 0.41 0.00 0.00 0.33 45 ^(a) ^(a) 12,345 1.16 3.4.A.8 0.40 0.000.00 0.33 45 ^(b) ^(b) 12,298 1.15 3.4.A.9 0.40 0.00 0.00 0.33 45 ^(a)^(a) 12,275 1.15 3.4.A.10 0.46 0.00 0.00 0.27 80 ^(b) ^(b) 21,608 1.393.4.A.11 0.46 0.00 0.00 0.21 112 ^(b) ^(b) 26,141 1.48 3.4.A.12 0.460.00 0.00 0.35 80 ^(b) ^(b) 20,529 1.37 3.4.A.13 0.46 0.00 0.00 0.29 114^(b) ^(b) 25,254 1.47 ^(a)PFA catalyst is prepared using the method ofexample H.1 wherein the catalytic component is biscyclopentadienylzirconium dimethyl and the activator component is N,N-dimethylaniliniumtetra(pentafluorophenyl)borate; ^(b)PFA catalyst is prepared using themethod of example H.2 wherein the catalytic component and activatorcomponent are prepared from the reaction of magnesium ethoxylate with anexcess of titanium tetrachloride; ^(c)efficiencies and polyolefinparticle sizes are in all cases evaluated using the method of example J.

TABLE 3.4.b Monomer, solvent and PNP solution charges for Example 3.4.B.Frag. Mon. 1 domain Butyl Mon. 2, PNP^(a) PNP Xylene in Total latexacrylate ALMA Xylene solution solution PNP weight of Example weight,weight, weight, weight, weight, wt % solution, xylene, Number gramsgrams grams grams grams PNP grams grams 3.4.B.1 498.9 22.90 1.21 48.2248.22 3.4.B.2 498.9 6.88 0.36 65.09 65.09 3.4.B.3 498.9 1.38 0.07 70.8870.88 3.4.B.4 498.9 68.71 3.62 0.00 0.00 3.4.B.5 374.1 34.35 1.81 72.3472.34 3.4.B.6 374.1 10.31 0.54 97.65 97.65 3.4.B.7 374.1 2.06 0.11106.33 106.33 3.4.B.8 374.1 103.08 5.43 0.00 0.00 3.4.B.9 498.88 22.901.21 48.22 48.22 3.4.B.10 498.88 22.90 1.21 48.22 48.22 3.4.B.11 498.8822.90 1.21 48.22 48.22 3.4.B.12 498.88 22.90 1.21 12.06 36.16 20 28.9340.99 3.4.B.13 498.88 22.90 1.21 12.06 36.17 40 21.70 33.76 3.4.B.14498.88 13.75 0.72 21.70 36.16 20 28.93 50.63 3.4.B.15 498.88 13.75 0.7221.70 36.17 40 21.70 43.4 ^(a)PNP is 2.C with composition MMA/ALMA =95/5 (weight basis).

TABLE 3.4.b.1 Characteristics of PFA particles varying in fragmentationzone size, amount, and crosslinking of second polymer, and PNP contentwherein the second polymer has a Tg below room termperature. mmolesgrams poly- residual mmoles mmoles Pore surface poly- olefin double OHepoxy volume area of olefin/ average PFA bonds/g groups/g groups/g ofPFA, PFA, metal gram P.S., Number PFA PFA PFA cc/g m²/g complexactivator PFA mm 3.4.B.1 0.41 0.00 0.00 0.33 45 ^(b) ^(b)  12,348^(c)1.16 3.4.B.2 0.45 0.00 0.00 0.50 40 ^(a) ^(a) 11,215 1.12 3.4.B.3 0.460.00 0.00 0.56 37 ^(b) ^(b) 10,588 1.10 3.4.B.4 0.35 0.00 0.00 0.00 50^(a) ^(a) 13,186 1.18 3.4.B.5 0.38 0.00 0.00 0.58 60 ^(b) ^(b) 16,3941.27 3.4.B.6 0.43 0.00 0.00 0.95 54 ^(a) ^(a) 14,907 1.23 3.4.B.7 0.450.00 0.00 1.12 43 ^(b) ^(b) 11,844 1.14 3.4.B.8 0.29 0.00 0.00 0.00 57^(b) ^(b) 14,845 1.23 3.4.B.9 0.41 0.00 0.00 0.33 45 ^(b) ^(b) 12,3481.16 3.4.B.10 0.41 0.00 0.00 0.33 45 ^(b) ^(b) 12,348 1.16 3.4.B.11 0.410.00 0.00 0.33 45 ^(a) ^(a) 12,348 1.16 3.4.B.12 0.41 0.00 0.00 0.27 80^(b) ^(b) 21,184 1.38 3.4.B.13 0.41 0.00 0.00 0.21 112 ^(b) ^(b) 25,6301.47 3.4.B.14 0.43 0.00 0.00 0.35 80 ^(b) ^(b) 20,270 1.36 3.4.B.15 0.430.00 0.00 0.29 114 ^(b) ^(b) 24,936 1.46 ^(a)PFA catalyst is preparedusing the method of example H.1 wherein the catalytic component isbiscyclopentadienyl zirconium dimethyl and the activator component isN,N-dimethylanilinium tetra(pentafluorophenyl)borate; ^(b)PFA catalystis prepared using the method of example H.2 wherein the catalyticcomponent and activator component are prepared from the reaction ofmagnesium ethoxylate with an excess of titanium tetrachloride;^(c)efficiencies and polyolefin particle sizes are in all casesevaluated using the method of example J.

TABLE 3.4.d PFAs having variations in functionalization of fragmentationdomain, second polymer, and PNP. PNP PNP Xylene in Total Mon. 1, Mon. 2,Mon. 3, Xylene solution solution PNP weight of Example weight, weight,weight, weight, weight, wt % solution, xylene, Number grams grams gramsgrams grams PNP grams grams styrene VBA DVB 3.4.D.1 6.96 1.63 2.26 97.6597.65 3.4.D.2 6.96 1.63 2.26 61.48 36.17^(a) 40 21.70 83.18 3.4.D.3 6.961.63 2.26 61.48 36.17^(b) 40 21.70 83.18 BA HEMA ALMA 3.4.D.4 8.86 1.630.54 97.65 97.65 3.4.D.5 8.86 1.63 0.54 61.48 36.17^(c) 40 21.70 83.183.4.D.6 8.86 1.63 0.54 61.48 36.17^(d) 40 21.70 83.18 styrene DVB3.4.D.7 8.59 2.26 61.48 36.17^(a) 40 21.70 83.18 3.4.D.8 8.59 2.26 61.4836.17^(b) 40 21.70 83.18 BA ALMA 3.4.D.9 10.31  0.54 61.48 36.17^(c) 4021.70 83.18 3.4.D.10 10.31  0.54 61.48 36.17^(d) 40 21.70 83.18 styreneVBA DVB 3.4.D.11 6.96 1.63 2.26 97.65 97.65 3.4.D.12 6.96 1.63 2.2661.48 36.17^(a) 40 21.70 83.18 3.4.D.13 6.96 1.63 2.26 61.48 36.17^(b)40 21.70 83.18 BA HEMA ALMA 3.4.D.14 8.86 1.63 0.54 97.65 97.65 3.4.D.158.86 1.63 0.54 61.48 36.17^(c) 40 21.70 83.18 3.4.D.16 8.86 1.63 0.5461.48 36.17^(d) 40 21.70 83.18 The fragmentation domain latex: forexamples 3.4.D.1–3.4.D.10 is the fragmentation latex of Example 1.1,weight = 374.1 grams; for examples 3.4.D.11–3.4.D.13 is Example 1.2.E,weight = 374.1 grams; and for examples 3.4.D.14–3.4.D.16 is Example1.2.A, weight = 374.1 grams. ^(a)PNP is example 2.A, 80 wt % styrene and20 wt % DVB, based on the weight of the PNP; ^(b)PNP is example 2.B, 65wt % styrene, 15 wt % AOH, and 20 wt % DVB; ^(c)PNP is example 2.C, 95wt % MMA and 5 wt % ALMA; ^(d)PNP is example 2.D, 80 wt % MMA, 15 wt %HEMA, and 5 wt % ALMA.

TABLE 3.4.d.1 Characteristics of PFA particles varying in fragmentationzone size, amount, and crosslinking of second polymer, and PNP contentwherein the second polymer has a Tg below room termperature. mmolesmmoles mmoles grams poly- residual OH epoxy Pore surface poly- olefindouble groups/ groups/ volume area of olefin/ average PFA bonds/g g g ofPFA, PFA, metal gram P.S., Number PFA PFA PFA cc/g m²/g complexactivator PFA mm 3.4.D.1 0.46 0.10 0.00 0.95 54 BBCZC^(a) MAO 15,694^(d) 1.25 3.4.D.2 0.46 0.09 0.00 0.76 97 BBCZC MAO 26,757 1.503.4.D.3 0.46 0.21 0.00 0.76 97 BBCZC MAO 28,021 1.52 3.4.D.4 0.43 0.100.00 0.95 54 BBCZC MAO 15,577 1.25 3.4.D.5 0.40 0.09 0.00 0.76 97 BBCZCMAO 26,203 1.49 3.4.D.6 0.40 0.22 0.00 0.76 97 BBCZC MAO 27,479 1.513.4.D.7 0.46 0.00 0.00 0.76 97 ^(c) ^(c) 25,845 1.48 3.4.D.8 0.46 0.120.00 0.76 97 BBCZC MAO 27,066 1.50 3.4.D.9 0.40 0.00 0.00 0.76 97 ^(b)^(b) 25,198 1.47 3.4.D.10 0.40 0.12 0.00 0.76 97 BBCZC MAO 26,426 1.493.4.D.11 0.46 1.01 0.00 0.95 54 BBCZC MAO 22,200 1.41 3.4.D.12 0.46 0.900.00 0.76 97 BBCZC MAO 36,457 1.66 3.4.D.13 0.46 1.02 0.00 0.76 97 BBCZCMAO 38,180 1.68 3.4.D.14 0.12 1.01 0.00 0.95 54 BBCZC MAO 19,561 1.353.4.D.15 0.12 0.90 0.00 0.76 97 BBCZC MAO 32,105 1.59 3.4.D.16 0.12 1.030.00 0.76 97 BBCZC MAO 33,668 1.61 ^(a)BBGZC is the metal complex(BuCp)2ZrCl2; ^(b)PFA catalyst is prepared using the method of exampleH.1 wherein the catalytic component is biscyclopentadienyl zirconiumdimethyl and the activator component is N,N-dimethylaniliniumtetra(pentafluorophenyl)borate; ^(c)PFA catalyst is prepared using themethod of example H.2 wherein the catalytic component and activatorcomponent are prepared from the reaction of magnesium ethoxylate with anexcess of titanium tetrachloride; ^(d)efficiencies and polyolefinparticle sizes are in all cases evaluated using the method of example J.

Example 4.1

Epoxidation of Vinyl Bearing PFAs Using m-chloroperbenzoic Acid (MCPBA).

A 500 ml narrow mouth glass bottle is charged with 5.0 grams of PFAparticles (screened to provide particles having diameters between 38 μmand 45 μm), and 150 grams of 1,2-dichloroethane. The bottle is placed ona laboratory shaker and agitated gently for 1 hour. The bottle is thenremoved and placed in an ice bath for 30 minutes. A solution is preparedconsisting of 20 ml of 1,2-dichloroethane and m-chloroperoxybenzoic acid(nominal 75% active) in one of the amounts given in grams reagent pergram of PFA, shown in Table 4.1.a, depending upon the desired number ofmmoles of MCPBA per mmole of vinyl group. This solution is rapidly addedto a cold reaction bottle, and the bottle is placed on the shaker andagitated gently for 20 hours. During this time the temperature of thereaction mixture rises to 30° C., primarily due to the heat generated bythe mechanism of the shaker.

The reaction mixture is poured into a 125 ml glass filter columnequipped with a fine porosity filter disk. The reaction solvent isremoved under vacuum, and the solid resin is mixed with 100 ml of1,2-dichloroethane, followed by removal under vacuum. This process isrepeated with two additional 100 ml portions of 1,2-dichloroethane. Thewash process is then repeated with three portions of inhibitor freetetrahydrofuran. The solid resin is then dried in the column under aflow of nitrogen, followed by drying at room temperature under vacuum.

TABLE 4.1.a MCPBA use level based on total moles of DVB present in PFAas polymerized units. mmole Grams of Epoxy vinyl MCPBA PFA PFA groups/added/ Example Example gram gram number number PFA PFA 4.1.A.1 3.1 0.450.085 4.1.A.2 3.1 0.45 0.057 4.1.A.3 3.2.H 2.04 0.032 4.1.A.4 3.3.G 2.040.377 4.1.A.5 3.3.H 2.04 0.032 4.1.A.6 3.4.A1 0.46 0.014 4.1.A.7 3.4.A20.46 0.085 4.1.A.8 3.4.A3 0.46 0.085 4.1.A.9 3.4.A4 0.46 0.085 4.1.A.103.4.A5 0.46 0.085 4.1.A.11 3.4.A6 0.46 0.113 4.1.A.12 3.4.A7 0.46 0.0764.1.A.13 3.4.A8 0.46 0.018 4.1.A.14 3.4.A9 0.46 0.074 4.1.A.15 3.4.A100.46 0.085 4.1.A.16 3.4.A11 0.46 0.085 4.1.A.17 3.4.A12 0.46 0.0854.1.A.18 3.4.A13 0.46 0.085 4.1.A.19 3.4.D.7 0.46 0.085 4.1.A.20 3.4.D.80.46 0.085 4.1.A.21 3.1 0.45 0.114

TABLE 4.1.a.1 Characteristics of PFA particles functionalized byepoxidation of the double bond bearing PFAs particles mmoles residualmmoles mmoles Pore surface grams double OH epoxy volume area of poly-poly-olefin PFA bonds/g groups/g groups/g of PFA, PFA, metal olefin/average Number PFA PFA PFA cc/g m²/g complex activator gram PFA P.S., mm4.1.A.1 0.46 0.00 0.37 0.33 45 BBCZC^(a) MAO  14,487^(b) 0.37 4.1.A.20.45 0.00 0.25 0.33 45 BBCZC MAO 13,805 0.36 4.1.A.3 0.17 0.00 0.14 0.3345 BBCZC MAO 11,840 0.34 4.1.A.4 2.05 0.00 1.64 0.33 22 BBCZC MAO 14,8740.37 4.1.A.5 0.17 0.00 0.14 0.33 22 BBCZC MAO  7,278 0.29 4.1.A.6 0.460.00 0.06 0.34 46 BBCZC MAO 12,914 1.17 4.1.A.7 0.46 0.00 0.37 0.50 40BBCZC MAO 13,001 1.18 4.1.A.8 0.46 0.00 0.37 0.56 37 BBCZC MAO 12,2081.15 4.1.A.9 0.47 0.00 0.37 0.58 60 BBCZC MAO 19,564 1.35 4.1.A.10 0.460.00 0.37 0.95 54 BBCZC MAO 17,388 1.30 4.1.A.11 0.46 0.00 0.43 1.12 43BBCZC MAO 14,325 1.21 4.1.A.12 0.41 0.00 0.33 0.33 45 BBCZC MAO 14,0011.21 4.1.A.13 0.40 0.00 0.08 0.33 45 BBCZC MAO 12,681 1.17 4.1.A.14 0.400.00 0.32 0.33 45 BBCZC MAO 13,858 1.20 4.1.A.15 0.46 0.00 0.37 0.27 80BBCZC MAO 24,900 1.46 4.1.A.16 0.46 0.00 0.37 0.21 112 BBCZC MAO 30,1241.56 4.1.A.17 0.46 0.00 0.37 0.35 80 BBCZC MAO 23,649 1.44 4.1.A.18 0.460.00 0.37 0.29 114 BBCZC MAO 29,091 1.54 4.1.A.19 0.46 0.00 0.37 0.76 97BBCZC MAO 29,769 1.55 4.1.A.20 0.46 0.00 0.37 0.76 97 BBCZC MAO 29,7691.55 4.1.A.21 0.45 0.00 0.44 0.33 45 BBCZC MAO 15,252 1.23 ^(a)BBCZC isthe metal complex (BuCp)₂ZrCl₂; ^(b)efficiencies and polyolefin particlesizes are in all cases evaluated using the method of example J.

Example G

Preparation of a Stock Solution of Catalytic Component (BuCp)₂ZrCl₂ andActivator Component Methylaluminoxane (MAO) in Toluene.

The manipulations of this example were carried out in a glovebox underdry Argon atmosphere. (BuCp)₂ZrCl₂ (˜9.5 mg) was placed in a 20 ml vial,followed by addition of 3.2 mls of 10% MAO solution in toluene. After 15minutes, the solution turned a pale yellow-orange color.

Example H

Standard Preparation of PFA Catalyst from a PFA. This Procedure was Usedto Prepare the PFA Catalysts.

The manipulations of this example are carried out in a glovebox underdry Argon atmosphere. The (100 mg) and 2 mls of toluene are charged to a20 ml vial to form a slurry. While shaking the slurry, 270 μl of(BuCp)₂ZrCl₂/MAO stock solution (˜20 μmole Zr/g of epoxidized resin) isadd to the slurry. After approximately 20 minutes, the PFA particlesbecomes yellow-orange while the solution becomes clear, indicating thatthe (BuCp)₂ZrCl₂/MAO is absorbed into the PFA. After 30 minutes, thetoluene is removed under reduced pressure during approximately one hourto yield a pale yellow powder. The powder (60 mgs) is then suspended in300 mls of heptane in a 600 ml Parr bomb sleeve. The sleeve is thensealed inside the Parr bomb which is pressurized to ˜40 psig with Argon.The Parr bomb is then removed from the glovebox and attached to theethylene system in preparation for an ethylene polymerization.

Example H.1

Preparation of a PFA Catalyst Containing Biscyclopentadienyl ZirconiumDimethyl as Catalytic Component and N,N-dimethylaniliniumtetra(pentafluorophenyl)borate as Activator Component.

An example illustrating preparation of a PFA catalyst comprising aspecific Group 4 catalyst of the present invention useful for thepolymerization and copolymerization of ethylene. All manipulations areperformed in a glove box under a dry and inert, argon atmosphere.

To 0.500 g of the PFA is added 5 ml of toluene. This PFA is allowed toimbibe toluene for 30 minutes. Next, a dark orange oil produced from thereaction of 0.053 g of biscyclopentadienyl zirconium dimethyl in 2 ml oftoluene with 0.145 g of N,N-dimethylaniliniumtetra(pentafluorophenyl)borate is added to the toluene swollen PFA. Theoil quickly reacts with the material resulting in a light orange productand a colorless toluene solution. After mixing for 45 minutes, thematerial is filtered and washed with 10 ml of toluene followed by 2×20ml of dry oxygen free heptane. A beige product resulted from filtrationand is dried under vacuum, yielding 0.580 g of catalyst. This productcontains a calculated 0.27 mmol of Zr per gram of PFA catalyst.

Example H.2

Preparation of a Pfa Catalyst Containing Ziegler-Natta Catalyst andActivator Components.

An example illustrating preparation of a PFA catalyst containingZiegler-Natta Catalyst and Activator components. All manipulations areperformed in a glove box under a dry and inert, argon atmosphere. To0.500 g of the PFA is added 5 ml of chlorobenzene. This PFA is allowedto imbibe chlorobenzene for 30 minutes, after which a solution ofmagnesium ethoxylate (0.11 g, 1.0 mmole) in 2 ml chlorobenzene is added.The mixture is stirred for 30 minutes, and then the chlorobenzene thatis not within the PFA is removed under vacuum. A solution of titaniumchloride (0.21 g, 1.1 mmole) in 5 ml chlorobenzene is then added to thePFA/Mg(OEt)₂. After mixing for 45 minutes, the material is filtered andwashed with 10 ml of toluene followed by 2×20 ml of dry oxygen freeheptane. The PFA catalyst is dried under vacuum, yielding 0.580 g ofcatalyst. This product contains a calculated 0.22 mmol of Ti per gram ofPFA catalyst.

Example J

Standard Ethylene Polymerization Procedure for Evaluating PFA Catalystsin a 600 ml Parr Reactor.

This procedure is used in all of the olefin polymerization examplesdescribed herein below. A 600 ml Parr reactor, including its inner glasssleeve, is dried overnight in an oven at ˜110° C., and then placed in aglovebox having an atmosphere of dry Argon. A pre-weighed quantity ofPFA catalyst, (typically ˜60 mg) is charged to the reactor sleeve, andthen 300 ml of dry, oxygen-free heptane is added to the sleeve as adiluent. The reactor is assembled and sealed, pressurized to 40 psigwith Argon, and then removed from the dry box. The reactor is thenplaced in a pre-heated heating mantle and connected to an ethylene feedline by means of a Swagelok quick-connect fitting. The connection isimmediately pressure purged ten times to 85 psig with ethylene. Thestirring shaft is then connected to the drive and stirring is commencedat about 200 rpm. While the reactor is warming to the targetpolymerization temperature, the water supply and discharge lines areconnected to the cooling coil. Once the reactor is at the targetpolymerization temperature, the Argon pressure is vented through theethylene connection through a 3-way valve with a check-protected vent.The reactor is then pressurized to 85 psig with ethylene, and maintainedat that pressure by means of a pressure regulator on the ethylenesupply. The ethylene feed is measured by a thermal flowmeter connectedto a data acquisition computer. Temperature is maintained within 3° C.of the target temperature by adjusting cooling water flow through thecooling coil. At the end of the desired polymerization batch time,ethylene flow is stopped, and the reactor is vented to atmosphericpressure. The reactor is then disassembled, and the product collected ona paper filter and washed with about 100 cc of methanol. The washedpolyethylene product is dried on the filter, followed by drying toconstant weight in a vacuum oven at 80° C. Results for particle size andefficiency of polyolefin production are given, along with PFAinformation, in several of the preceding tables of this experimentalsection.

1. A precision fragmentation assemblage wherein said assemblagecomprises: (A) a plurality of fragmentation domains; (B) one or morefragmentation zones; wherein said fragmentation domain comprises atleast one first polymer; and wherein said fragmentation zone comprises:(i) one or more connecting phases; (ii) optionally, one or more porephases; and (ii) optionally plural polymeric nanoparticles; and wherein:said connecting phase comprises at least one second polymer; said secondpolymer comprises at least one multi-ethylenically unsaturated monomer,present as polymerized units, in an amount of at least 0.05 percent byweight to 100 percent by weight, based on the weight of said secondpolymer; and said nanoparticles comprise at least one third polymer; and(C) one or more tether groups covalently bound to a polymeric chain,wherein said polymeric chain is a chain selected from the groupconsisting of said first polymer, said second polymer, said thirdpolymer, and combinations thereof.
 2. The precision fragmentationassemblage of claim 1, wherein said tether group comprises a functionalgroup selected from the group consisting of epoxy, vinyl, allyl, primaryamino, secondary amino, imino, amide, imide, aziridinyl, hydrazide,amidino, hydroxy, hydroperoxy, carboxyl, formyl, methoxycarbonyl,carbamoyl, sulfone, sulfine, sulfeno, thiol, thiocarboxyl, thioformyl,pyrrolyl, imidazolyl, piperidyl, indazolyl, carbazolyl, and combinationsthereof.
 3. A precision fragmentation assemblage catalyst, wherein saidcatalyst comprises: (A) a precision fragmentation assemblage; and (B) atleast one catalytic component; wherein said precision fragmentationassemblage comprises: (i) a plurality of fragmentation domains; and (ii)one or more fragmentation zones; wherein said fragmentation domaincomprises at least one first polymer; and wherein said fragmentationzone comprises at least one connecting phase, said connecting phasecomprising at least one second polymer, said second polymer comprisingat least one multi-ethylenically unsaturated second monomer, present aspolymerized units, in an amount from 0.05 percent by weight to 100percent by weight, based on the weight of the second polymer.
 4. Thecatalyst of claim 3, wherein said catalyst further comprises at leastone activator component.
 5. The catalyst composition of claim 4, whereinsaid activator component is an activator component selected from thegroup consisting of organoaluminum compounds, organoaluminoxanecompounds, hydroxyaluminoxanes, aluminoxinates, organic boranecompounds, inorganic borane compounds, borate anions, and mixturesthereof.
 6. The catalyst of claim 3, wherein said fragmentation domainhas an average particle size of at least 0.002 microns to no more than20 microns.
 7. The catalyst of claim 3, wherein said fragmentation zonefurther comprises at least one pore phase.
 8. The catalyst of claim 3,wherein said fragmentation zone further comprises plural polymericnanoparticles comprising at least one third polymer.
 9. The catalyst ofclaim 8, further comprising one or more tether groups covalently boundto a polymeric chain, wherein said polymeric chain is a chain selectedfrom the group consisting of said first polymer, said second polymer,said third polymer, and combinations thereof.
 10. The catalyst of claim9, wherein said tether group comprises a functional group selected fromthe group consisting of epoxy, vinyl, allyl, primary amino, secondaryamino, imino, amide, imide, aziridinyl, hydrazide, amidino, hydroxy,hydroperoxy, carboxyl, formyl, methoxycarbonyl, carbamoyl, sulfone,sulfine, sulfeno, thiol, thiocarboxyl, thioformyl, pyrrolyl, imidazolyl,piperidyl, indazolyl, carbazolyl, and combinations thereof.
 11. Thecatalyst of claim 3, further comprising one or more tether groupscovalently bound to a polymeric chain, wherein said polymeric chain is achain selected from the group consisting of said first polymer, saidsecond polymer, and combinations thereof.
 12. The catalyst of claim 11,wherein said tether group comprises a functional group selected from thegroup consisting of epoxy, vinyl, allyl, primary amino, secondary amino,imino, amide, imide, aziridinyl, hydrazide, amidino, hydroxy,hydroperoxy, carboxyl, formyl, methoxycarbonyl, carbamoyl, sulfone,sulfine, sulfeno, thiol, thiocarboxyl, thioformyl, pyrrolyl, imidazolyl,piperidyl, indazolyl, carbazolyl, and combinations thereof.
 13. Thecatalyst of claim 3, wherein said catalytic component is anorganometallic catalyst based on a metal, wherein said metal is a metalselected from the group consisting of metals of Group 3-11, lanthanidemetals, actinide metals, and combinations thereof.
 14. An olefinpolymerization process, wherein said olefin polymerization processcomprises: (A) contacting at least one olefin monomer with at least oneprecision fragmentation assemblage catalyst; (B) polymerizing saidolefin monomer to produce a polyolefin; (C) isolating said polyolefin,wherein said catalyst comprises: (i) a precision fragmentationassemblage; and (ii) at least one catalytic component; wherein saidprecision fragmentation assemblage comprises: (a) a plurality offragmentation domains; and (b) one or more fragmentation zones; whereinsaid fragmentation domain comprises at least one first polymer; andwherein said fragmentation zone comprises at least one connecting phase,said connecting phase comprising at least one second polymer, saidsecond polymer comprising at least one multi-ethylenically unsaturatedmonomer, present as polymerized units, in an amount of at least 0.05percent by weight to 100 percent by weight, based on the weight of saidsecond polymer.
 15. The precision fragmentation assemblage of claim 1,further comprising an active ingredient.
 16. The precision fragmentationassemblage of claim 15, wherein said active ingredient is selected frompharmaceuticals, biocides, herbicides, mildewcides, insecticides,fungicides, fertilizers, cosmetics, fragrances, liquid crystals,colorants, enzymes, or combinations thereof.